U.S. patent number 9,549,560 [Application Number 14/517,442] was granted by the patent office on 2017-01-24 for pesticidal compositions and related methods.
This patent grant is currently assigned to Dow AgroSciences LLC. The grantee listed for this patent is DOW AGROSCIENCES LLC. Invention is credited to Ann M. Buysse, Negar Garizi, Ricky Hunter, Daniel Knueppel, Asako Kubota, Noormohamed M. Niyaz, Tony K. Trullinger, Martin J. Walsh, Yu Zhang.
United States Patent |
9,549,560 |
Walsh , et al. |
January 24, 2017 |
Pesticidal compositions and related methods
Abstract
A pesticidal composition comprises at least one compound
selected from a 1-(3-pyridyl-N-oxide) pyrazole compound of formula
I, II, or III, or any agriculturally acceptable salt thereof,
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.12, R.sub.13, Y, and Q, are as described
herein. A method of controlling pests comprises applying the
pesticidal composition near a population of pests. ##STR00001##
Inventors: |
Walsh; Martin J. (Carmel,
IN), Knueppel; Daniel (Zionsville, IN), Niyaz;
Noormohamed M. (Indianapolis, IN), Buysse; Ann M.
(Carmel, IN), Garizi; Negar (Westfield, IN), Kubota;
Asako (Indianapolis, IN), Zhang; Yu (Carmel, IN),
Hunter; Ricky (Westfield, IN), Trullinger; Tony K.
(Westfield, IN) |
Applicant: |
Name |
City |
State |
Country |
Type |
DOW AGROSCIENCES LLC |
Indianapolis |
IN |
US |
|
|
Assignee: |
Dow AgroSciences LLC
(Indianapolis, IN)
|
Family
ID: |
52826660 |
Appl.
No.: |
14/517,442 |
Filed: |
October 17, 2014 |
Prior Publication Data
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Document
Identifier |
Publication Date |
|
US 20150111733 A1 |
Apr 23, 2015 |
|
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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61894336 |
Oct 22, 2013 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C05G
3/60 (20200201); A01N 47/20 (20130101); C07D
401/04 (20130101); A01N 43/56 (20130101) |
Current International
Class: |
A01N
47/20 (20060101); C07D 401/04 (20060101); C05G
3/02 (20060101); A01N 43/56 (20060101); C07D
401/02 (20060101) |
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Other References
PCT International Search Report; PCT/US2014/061069; dated Jan. 15,
2015. cited by applicant .
PCT Written Opinion PCT/US2014/061069; dated Jan. 15, 2015. cited
by applicant.
|
Primary Examiner: Oswecki; Jane C
Attorney, Agent or Firm: Corvin; Carl D. Magleby Cataxinos
& Greenwood
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent
Application Ser. No. 61/894,336, filed Oct. 22, 2013, the
disclosure of which is hereby incorporated herein in its entirety
by this reference.
Claims
We claim:
1. A pesticidal composition, comprising
1-(3-pyridyl-N-oxide)pyrazole compound of formula I or any
agriculturally acceptable salt thereof: ##STR00268## wherein: (a)
R.sub.1, R.sub.2, and R.sub.4 are independently selected from H, F,
Cl, Br, I, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, or
substituted or unsubstituted C.sub.1-C.sub.6 haloalkyl, wherein
each said R.sub.1, R.sub.2, and R.sub.4, when substituted, has one
or more substituents selected from F, Cl, Br, I, CN, NO.sub.2,
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.10 cycloalkyl, or C.sub.3-C.sub.10
halocycloalkyl, each of which is substituted, unsubstituted, or
substituted with R.sub.11; (b) R.sub.3 is selected from H, F, Cl,
Br, I, CN, NO.sub.2, substituted or unsubstituted C.sub.1-C.sub.6
alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl,
substituted or unsubstituted C.sub.1-C.sub.6 alkoxy, substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkyl, substituted or
unsubstituted C.sub.1-C.sub.6 haloalkyl, substituted or
unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, OR.sub.11, C(.dbd.X.sub.1)R.sub.11,
C(.dbd.X.sub.1)OR.sub.11, C(.dbd.X.sub.1)N(R.sub.11).sub.2,
N(R.sub.11).sub.2, N(R.sub.11)C(.dbd.X.sub.1)R.sub.11, SR.sub.11,
S(O).sub.nOR.sub.11, or R.sub.11S(O).sub.nR.sub.11, wherein each
said R.sub.3, when substituted, has one or more substituents
selected from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10
halocycloalkenyl, OR.sub.11, S(O).sub.nOR.sub.11, C.sub.6-C.sub.20
aryl, or C.sub.1-C.sub.20 heterocyclyl, each of which is
substituted, unsubstituted, or substituted with R.sub.11; (c)
R.sub.5 is H, F, Cl, Br, I, CN, NO.sub.2, substituted or
unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted
C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.10 cycloalkyl, substituted or
unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, OR.sub.11, C(.dbd.X.sub.1)R.sub.11,
C(.dbd.X.sub.1)OR.sub.11, C(.dbd.X.sub.1)N(R.sub.11).sub.2,
N(R.sub.11).sub.2, N(R.sub.11)C(.dbd.X.sub.1)R.sub.11, SR.sub.11,
S(O).sub.nOR.sub.11, or R.sub.11S(O).sub.nR.sub.11, wherein each
said R.sub.5, when substituted, has one or more substituents
selected from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10
halocycloalkenyl, OR.sub.11, S(O).sub.nOR.sub.11, C.sub.6-C.sub.20
aryl, or C.sub.1-C.sub.20 heterocyclyl, each of which is
substituted, unsubstituted, or substituted with R.sub.11; (d)
R.sub.6 is H, F, Cl, Br, I, substituted or unsubstituted
C.sub.1-C.sub.6 alkyl, or C.sub.1-C.sub.6 haloalkyl, wherein each
said R.sub.6, when substituted, has one or more substituents
selected from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3-C.sub.10 halocycloalkyl, or C.sub.3-C.sub.10
halocycloalkenyl; (e) R.sub.7 is selected from H, substituted or
unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted
C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted
C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted
C.sub.1-C.sub.6 alkoxy, substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkyl, substituted or unsubstituted
C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, C.sub.1-C.sub.6 alkyl
C.sub.6-C.sub.20 aryl wherein the alkyl and aryl is independently
substituted or unsubstituted, C.sub.1-C.sub.6
alkyl-(C.sub.3-C.sub.10 cyclohaloalkyl) wherein the alkyl and
cyclohaloalkyl is independently substituted or unsubstituted,
C.sub.1-C.sub.6 alkyl-(C.sub.3-C.sub.10 cycloalkyl) wherein the
alkyl and cycloalkyl is independently substituted or unsubstituted,
wherein each said R.sub.7, when substituted, has one or more
substituents selected from F, Cl, Br, I, CN, NO.sub.2,
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6
alkynyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6 haloalkenyl,
C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6 haloalkenyloxy,
C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 cycloalkenyl,
C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10 halocycloalkenyl,
OR.sub.11, S(O).sub.nOR.sub.11, C.sub.6-C.sub.20 aryl, or
C.sub.1-C.sub.20 heterocyclyl, or R.sub.11aryl, each of which is
substituted, unsubstituted, or substituted with R.sub.11; (f)
R.sub.8 is R.sub.9S(O).sub.nR.sub.10 or R.sub.9S(O).sub.nH; (g)
R.sub.9 is substituted or unsubstituted C.sub.2-C.sub.12 alkenyl,
substituted or unsubstituted C.sub.1-C.sub.12 alkyl, or substituted
or unsubstituted C.sub.3-C.sub.10 cycloalkyl, wherein each said
R.sub.9, when substituted, has one or more substituents selected
from F, Cl, Br, I, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.10 cycloalkyl,
C.sub.3-C.sub.10 halocycloalkyl, OR.sub.11, S(O).sub.nR.sub.11,
C.sub.6-C.sub.20 aryl, or C.sub.1-C.sub.20 heterocyclyl, each of
which is substituted, unsubstituted, or substituted with R.sub.11;
(h) R.sub.10 is selected from substituted or unsubstituted
C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6
alkenyl, substituted or unsubstituted C.sub.1-C.sub.6 alkoxy,
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl,
substituted or unsubstituted C.sub.3-C.sub.10 halocycloalkyl
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl,
substituted or unsubstituted C.sub.6-C.sub.20 aryl, or substituted
or unsubstituted C.sub.1-C.sub.20 heterocyclyl, wherein each said
R.sub.10, when substituted, has one or more substituents selected
from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3 -C.sub.10 halocycloalkyl, C.sub.3-C.sub.10
halocycloalkenyl, oxo, OR.sub.11, S(O).sub.nR.sub.11,
C.sub.6-C.sub.20 aryl, or C.sub.1-C.sub.20 heterocyclyl, each of
which is substituted, unsubstituted, or substituted with R.sub.11;
(i) R.sub.11 is, each independently, selected from H, R.sub.8, CN,
substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or
unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted
C.sub.1-C.sub.6 alkoxy, substituted or unsubstituted
C.sub.2-C.sub.6 alkenyloxy, substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkyl, substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkenyl, substituted or unsubstituted
C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, substituted or unsubstituted
S(O).sub.nC.sub.1-C.sub.6 alkyl, or substituted or unsubstituted
N(C.sub.1-C.sub.6 alkyl).sub.2, wherein each said R.sub.11, when
substituted, has one or more substituents selected from F, Cl, Br,
I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6 haloalkenyl,
C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6 haloalkenyloxy,
C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 cycloalkenyl,
C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10 halocycloalkenyl,
OC.sub.1-C.sub.6 alkyl, OC.sub.1-C.sub.6 haloalkyl,
S(O).sub.nC.sub.1-C.sub.6 alkyl, S(O).sub.nOC.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.20 aryl, or C.sub.1-C.sub.20 heterocyclyl; (j) Q is
O, S or S(.dbd.O).sub.n; (k) X.sub.1 is O or S; and (l) n is 0, 1
or 2.
2. The composition of claim 1, wherein R.sub.1, R.sub.2, and
R.sub.4 are H.
3. The composition of claim 1, wherein R.sub.3 is selected from H,
F, Cl, Br, or I.
4. The composition of claim 1, wherein R.sub.3 is H or F.
5. The composition of claim 1, wherein R.sub.5 is selected from F,
Cl, Br, I, or unsubstituted C.sub.1-C.sub.6 alkyl.
6. The composition of claim 1, wherein R.sub.5 is Cl or
CH.sub.3.
7. The composition of claim 1, wherein R.sub.6 is H.
8. The composition of claim 1, wherein R.sub.7 is selected from H,
CH.sub.3, CH.sub.2CH.sub.3 CH.sub.2C.ident.CH, or
CH(CH.sub.3)C.ident.CH.
9. The composition of claim 1, wherein R.sub.8 is selected from
C.sub.1-C.sub.6 alkyl-S(O).sub.nCH.sub.2(unsubstituted
C.sub.3-C.sub.10 halocycloalkyl), C.sub.1-C.sub.6
alkyl-S(O).sub.nC.sub.3-C.sub.6 haloalkyl wherein said halos are
only on the carbon atom furthest from the sulfur atom.
10. The composition of claim 1, wherein R.sub.8 is selected from
C.sub.1-C.sub.4 alkyl-S--CH.sub.2-halocyclopropyl or
CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CF.sub.3.
11. The composition of claim 1, wherein n is 0 or 1.
12. The composition of claim 1, further comprising: (a) one or more
compounds having acaricidal, algicidal, avicidal, bactericidal,
fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal,
rodenticidal, or virucidal properties; or (b) one or more compounds
that are antifeedants, bird repellents, chemosterilants, herbicide
safeners, insect attractants, insect repellents, mammal repellents,
mating disrupters, plant activators, plant growth regulators, or
synergists; or (c) both (a) and (b).
13. The composition of claim 1, further comprising one or more
compounds selected from: (3-ethoxypropyl)mercury bromide,
1,2-dichloropropane, 1,3-dichloropropene, 1-methylcyclopropene,
1-naphthol, 2-(octylthio)ethanol, 2,3,5-tri-iodobenzoic acid,
2,3,6-TBA, 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium,
2,3,6-TBA-potassium, 2,3,6-TBA-sodium, 2,4,5-T,
2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl,
2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl,
2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl,
2,4,5-T-isopropyl, 2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,
2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,
2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,
2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,
2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,
2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,
2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP,
2,4-D-ethyl, 2,4-D-heptylamrnonium, 2,4-D-isobutyl, 2,4-D-isoctyl,
2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium,
2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl,
2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl,
2,4-D-tetradecylammonium, 2,4-D-triethylammonium,
2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 2iP,
2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, 3,4-DB,
3,4-DP, 4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPA-sodium,
4-CPB, 4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline
sulfate, 8-phenylmercurioxyquinoline, abamectin, abscisic acid,
ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor,
acetophos, acetoprole, acibenzolar, acibenzolar-S-methyl,
acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen,
acrep, acrinathrin, acrolein, acrylonitrile, acypetacs,
acypetacs-copper, acypetacs-zinc, alachlor, alanycarb, albendazole,
aldicarb, aldimorph, aldoxycarb, aldrin, allethrin, allicin,
allidochlor, allosamidin, alloxydim, alloxydim-sodium, allyl
alcohol, allyxycarb, alorac, alpha-cypermethrin, alpha-endosulfan,
ametoctradin, ametridione, ametryn, amibuzin, amicarbazone,
amicarthiazol, amidithion, amidoflumet, amidosulfuron, aminocarb,
aminocyclopyrachlor, amino cyclopyrachlor-methyl,
aminocyclopyrachlor-potassium, aminopyralid,
aminopyralid-potassium, aminopyralid-tris(2-hydroxypropyl)ammonium,
amiprofos-methyl, amiprophos, amisulbrom, amiton, amiton oxalate,
amitraz, amitrole, ammonium sulfamate, ammonium
.alpha.-naphthaleneacetate, amobam, ampropylfos, anabasine,
ancymidol, anilazine, anilofos, anisuron, anthraquinone, antu,
apholate, aramite, arsenous oxide, asomate, aspirin, asulam,
asulam-potassium, asulam-sodium, athidathion, atraton, atrazine,
aureofungin, aviglycine, aviglycine hydrochloride, azaconazole,
azadirachtin, azafenidin, azamethiphos, azimsulfuron,
azinphos-ethyl, azinphos-methyl, aziprotryne, azithiram,
azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh,
barban, barium hexafluorosilicate, barium polysulfide, barthrin,
BCPC, beflubutamid, benalaxyl, benalaxyl-M, benazolin,
benazolin-dimethylammonium, benazolin-ethyl, benazolin-potassium,
bencarbazone, benclothiaz, bendiocarb, benfluralin, benfuracarb,
benfuresate, benodanil, benomyl, benoxacor, benoxafos, benquinox,
bensulfuron, bensulfuron-methyl, bensulide, bensultap, bentaluron,
bentazone, bentazone-sodium, benthiavalicarb,
benthiavalicarb-isopropyl, benthiazole, bentranil, benzadox,
benzadox-ammonium, benzalkonium chloride, benzamacril,
benzamacril-isobutyl, benzamorf, benzfendizone, benzipram,
benzobicyclon, benzofenap, benzofluor, benzohydroxamic acid,
benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzyl
benzoate, benzyladenine, berberine, berberine chloride,
beta-cyfluthrin, beta-cypermethrin, bethoxazin, bicyclopyrone,
bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos,
bilanafos-sodium, binapacryl, bingqingxiao, bioallethrin,
bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bisazir,
bismerthiazol, bispyribac, bispyribac-sodium, bistrifluron,
bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeaux
mixture, boric acid, boscalid, brassinolide, brassinolide-ethyl,
brevicomin, brodifacoum, brofenvalerate, brofluthrinate, bromacil,
bromacil-lithium, bromacil-sodium, bromadiolone, bromethalin,
bromethrin, bromfenvinfos, bromoacetamide, bromobonil, bromobutide,
bromocyclen, bromo-DDT, bromofenoxim, bromophos, bromophos-ethyl,
bromopropylate, bromothalonil, bromoxynil, bromoxynil butyrate,
bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium,
brompyrazon, bromuconazole, bronopol, bucarpolate, bufencarb,
buminafos, bupirimate, buprofezin, Burgundy mixture, busulfan,
butacarb, butachlor, butafenacil, butamifos, butathiofos,
butenachlor, butethrin, buthidazole, buthiobate, buthiuron,
butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin,
butroxydim, buturon, butylamine, butylate, cacodylic acid,
cadusafos, cafenstrole, calcium arsenate, calcium chlorate, calcium
cyanamide, calcium polysulfide, calvinphos, cambendichlor,
camphechlor, camphor, captafol, captan, carbamorph, carbanolate,
carbaryl, carbasulam, carbendazim, carbendazim benzenesulfonate,
carbendazim sulfite, carbetamide, carbofuran, carbon disulfide,
carbon tetrachloride, carbophenothion, carbosulfan, carboxazole,
carboxide, carboxin, carfentrazone, carfentrazone-ethyl,
carpropamid, cartap, cartap hydrochloride, carvacrol, carvone,
CDEA, cellocidin, CEPC, ceralure, Cheshunt mixture, chinomethionat,
chitosan, chlobenthiazone, chlomethoxyfen, chloralose, chloramben,
chloramben-ammonium, chloramben-diolamine, chloramben-methyl,
chloramben-methylammonium, chloramben-sodium, chloramine
phosphorus, chloramphenicol, chloraniformethan, chloranil,
chloranocryl, chlorantraniliprole, chlorazifop,
chlorazifop-propargyl, chlorazine, chlorbenside, chlorbenzuron,
chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone,
chlordimeform, chlordimeform hydrochloride, chlorempenthrin,
chlorethoxyfos, chloreturon, chlorfenac, chlorfenac-ammonium,
chlorfenac-sodium, chlorfenapyr, chlorfenazole, chlorfenethol,
chlorfenprop, chlorfenson, chlorfensulphide, chlorfenvinphos,
chlorfluazuron, chlorflurazole, chlorfluren, chlorfluren-methyl,
chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron,
chlorimuron-ethyl, chlormephos, chlormequat, chlormequat chloride,
chlomidine, chlomitrofen, chlorobenzilate,
chlorodinitronaphthalenes, chloroform, chloromebuform,
chloromethiuron, chloroneb, chlorophacinone,
chlorophacinone-sodium, chloropicrin, chloropon, chloropropylate,
chlorothalonil, chlorotoluron, chloroxuron, chloroxynil,
chlorphonium, chlorphonium chloride, chlorphoxim, chlorprazophos,
chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl,
chlorquinox, chlorsulfuron, chlorthal, chlorthal-dimethyl,
chlorthal-monomethyl, chlorthiamid, chlorthiophos, chlozolinate,
choline chloride, chromafenozide, cinerin I, cinerin II, cinerins,
cinidon-ethyl, cinmethylin, cinosulfuron, ciobutide, cisanilide,
cismethrin, clethodim, climbazole, cliodinate, clodinafop,
clodinafop-propargyl, cloethocarb, clofencet, clofencet-potassium,
clofentezine, clofibric acid, clofop, clofop-isobutyl, clomazone,
clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,
clopyralid-olamine, clopyralid-potassium,
clopyralid-tris(2-hydroxypropyl)ammonium, cloquintocet,
cloquintocet-mexyl, cloransulam, cloransulam-methyl, closantel,
clothianidin, clotrimazole, cloxyfonac, cloxyfonac-sodium, CMA,
codlelure, colophonate, copper acetate, copper acetoarsenite,
copper arsenate, copper carbonate, basic, copper hydroxide, copper
naphthenate, copper oleate, copper oxychloride, copper silicate,
copper sulfate, copper zinc chromate, coumachlor, coumafuryl,
coumaphos, coumatetralyl, coumithoate, coumoxystrobin, CPMC, CPMF,
CPPC, credazine, cresol, crimidine, crotamiton, crotoxyphos,
crufomate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam,
cuprous oxide, curcumenol, cyanamide, cyanatryn, cyanazine,
cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyazofamid,
cybutryne, cyclafuramid, cyclanilide, cyclethrin, cycloate,
cycloheximide, cycloprate, cycloprothrin, cyclosulfamuron,
cycloxydim, cycluron, cyenopyrafen, cyflufenamid, cyflumetofen,
cyfluthrin, cyhalofop, cyhalofop-butyl, cyhalothrin, cyhexatin,
cymiazole, cymiazole hydrochloride, cymoxanil, cyometrinil,
cypendazole, cypermethrin, cyperquat, cyperquat chloride,
cyphenothrin, cyprazine, cyprazole, cyproconazole, cyprodinil,
cyprofuram, cypromid, cyprosulfamide, cyromazine, cythioate,
daimuron, dalapon, dalapon-calcium, dalapon-magnesium,
dalapon-sodium, daminozide, dayoutong, dazomet, dazornet-sodium,
DBCP, d-camphor, DCIP, DCPTA, DDT, debacarb, decafentin,
decarbofuran, dehydroacetic acid, delachlor, deltamethrin,
demephion, demephion-O, demephion-S, demeton, demeton-methyl,
demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl,
demeton-S-methylsulphon, desmedipham, desmetryn,
d-fanshiluquebingjuzhi, diafenthiuron, dialifos, di-allate,
diamidafos, diatomaceous earth, diazinon, dibutyl phthalate,
dibutyl succinate, dicamba, dicamba-diglycolamine,
dicamba-dimethylammonium, dicamba-diolamine,
dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine,
dicamba-potassium, dicamba-sodium, dicamba-trolamine, dicapthon,
dichlobenil, dichlofenthion, dichlofluanid, dichlone,
dichloralurea, dichlorbenzuron, dichlorflurenol,
dichlorflurenol-methyl, dichlormate, dichlormid, dichlorophen,
dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl,
dichlorprop-dimethylammonium, dichlorprop-ethylammonium,
dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,
dichlorprop-P-2-ethylhexyl, dichlorprop-P-dimethylammonium,
dichlorprop-potassium, dichlorprop-sodium, dichlorvos,
dichlozoline, diclobutrazol, diclocymet, diclofop, diclofop-methyl,
diclomezine, diclomezine-sodium, dicloran, diclosulam, dicofol,
dicoumarol, dicresyl, dicrotophos, dicyclanil, dicyclonon,
dieldrin, dienochlor, diethamquat, diethamquat dichloride,
diethatyl, diethatyl-ethyl, diethofencarb, dietholate, diethyl
pyrocarbonate, diethyltoluamide, difenacoum, difenoconazole,
difenopenten, difenopenten-ethyl, difenoxuron, difenzoquat,
difenzoquat metilsulfate, difethialone, diflovidazin,
diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr-sodium,
diflumetorim, dikegulac, dikegulac-sodium, dilor, dimatif,
dimefluthrin, dimefox, dimefuron, dimepiperate, dimetachlone,
dimetan, dimethacarb, dimethachlor, dimethametryn, dimethenamid,
dimethenamid-P, dimethipin, dimethirirnol, dimethoate,
dimethomorph, dimethrin, dimethyl carbate, dimethyl phthalate,
dimethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin,
dinex, dinex-diclexine, dingjunezuo, diniconazole, diniconazole-M,
dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton,
dinofenate, dinopenton, dinoprop, dinosaur, dinoseb, dinoseb
acetate, dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium,
dinoseb-trolamine, dinosulfon, dinotefuran, dinoterb, dinoterb
acetate, dinoterbon, diofenolan, dioxabenzofos, dioxacarb,
dioxathion, diphacinone, diphacinone-sodium, diphenamid, diphenyl
sulfone, diphenylamine, dipropalin, dipropetryn, dipyrithione,
diquat, diquat dibromide, disparlure, disul, disulfiram,
disulfoton, disul-sodium, ditalimfos, dithianon, dithicrofos,
dithioether, dithiopyr, diuron, d-limonene, DMPA, DNOC,
DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph
acetate, dodemorph benzoate, dodicin, dodicin hydrochloride,
dodicin-sodium, dodine, dofenapyn, dominicalure, doramectin,
drazoxolon, DSMA, dufulin, EBEP, EBP, ecdysterone, edifenphos,
eglinazine, eglinazine-ethyl, emamectin, emamectin benzoate, EMPC,
empenthrin, endosulfan, endothal, endothal-diammonium,
endothal-dipotassium, endothal-disodium, endothion, endrin,
enestroburin, EPN, epocholeone, epofenonane, epoxiconazole,
eprinomectin, epronaz, EPTC, erbon, ergocalciferol,
erlujixiancaoan, esdepallethrine, esfenvalerate, esprocarb,
etacelasil, etaconazole, etaphos, etem, ethaboxam, ethachlor,
ethalfluralin, ethametsulfuron, ethametsulfuron-methyl,
ethaprochlor, ethephon, ethidimuron, ethiofencarb, ethiolate,
ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl,
ethofumesate, ethohexadiol, ethoprophos, ethoxyfen,
ethoxyfen-ethyl, ethoxyquin, ethoxysulfuron, ethychlozate, ethyl
formate, ethyl .alpha.-naphthaleneacetate, ethyl-DDD, ethylene,
ethylene dibromide, ethylene dichloride, ethylene oxide, ethylicin,
ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate,
ethylmercury bromide, ethylmercury chloride, ethylmercury
phosphate, etinofen, etnipromid, etobenzanid, etofenprox,
etoxazole, etridiazole, etrimfos, eugenol, EXD, famoxadone,
famphur, fenamidone, fenaminosulf, fenamiphos, fenapanil,
fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole,
fenbutatin oxide, fenchlorazole, fenchlorazole-ethyl, fenchlorphos,
fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid,
fenitropan, fenitrothion, fenjuntong, fenobucarb, fenoprop,
fenoprop-3-butoxypropyl, fenoprop-butometyl, fenoprop-butotyl,
fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl,
fenoprop-potassium, fenothiocarb, fenoxacrim, fenoxanil,
fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl,
fenoxasulfone, fenoxycarb, fenpiclonil, fenpirithrin,
fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine,
fenpyroximate, fenridazon, fenridazon-potassium, fenridazon-propyl,
fenson, fensulfothion, fenteracol, fenthiaprop, fenthiaprop-ethyl,
fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride,
fentin hydroxide, fentrazamide, fentrifanil, fenuron, fenuron TCA,
fenvalerate, ferbam, ferimzone, ferrous sulfate, fipronil,
flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl,
flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron,
flocoumafen, flometoquin, flonicamid, florasulam, fluacrypyrim,
fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P,
fluazifop-P-butyl, fluazinam, fluazolate, fluazuron, flubendiamide,
flubenzimine, flucarbazone, flucarbazone-sodium, flucetosulfuron,
fluchloralin, flucofuron, flucycloxuron, flucythrinate,
fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerim,
flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr-ethyl,
flufiprole, flumethrin, flumetover, flumetralin, flumetsulam,
flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin,
flumipropyn, flumorph, fluometuron, fluopicolide, fluopyram,
fluorbenside, fluoridamid, fluoroacetamide, fluorodifen,
fluoroglycofen, fluoroglycofen-ethyl, fluoroimide, fluoromidine,
fluoronitrofen, fluothiuron, fluotrimazole, fluoxastrobin,
flupoxam, flupropacil, flupropadine, flupropanate,
flupropanate-sodium, flupyradifurone, flupyrsulfuron,
flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium,
fluquinconazole, flurazole, flurenol, flurenol-butyl,
flurenol-methyl, fluridone, flurochloridone, fluroxypyr,
fluroxypyr-butometyl, fluroxypyr-meptyl, flurprimidol, flursulamid,
flurtamone, flusilazole, flusulfamide, fluthiacet,
fluthiacet-methyl, flutianil, flutolanil, flutriafol, fluvalinate,
fluxapyroxad, fluxofenim, folpet, fomesafen, fomesafen-sodium,
fonofos, foramsulfuron, forchlorfenuron, formaldehyde, formetanate,
formetanate hydrochloride, formothion, formparanate, formparanate
hydrochloride, fosamine, fosamine-ammonium, fosetyl,
fosetyl-aluminium, fosmethilan, fospirate, fosthiazate, fosthietan,
frontalin, fuberidazole, fucaojing, fucaomi, funaihecaoling,
fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr,
furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin,
furfural, furilazole, furmecyclox, furophanate, furyloxyfen,
gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid,
gibberellins, gliftor, glufosinate, glufosinate-ammonium,
glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium,
glyodin, glyoxime, glyphosate, glyphosate-diammonium,
glyphosate-dimethylammonium, glypho sate-isopropylammonium,
glyphosate-monoammonium, glyphosate-potassium,
glyphosate-sesquisodium, glyphosate-trimesium, glyphosine,
gossyplure, grandlure, griseofulvin, guazatine, guazatine acetates,
halacrinate, halfenprox, halofenozide, halosafen, halosulfuron,
halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl,
haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl,
haloxyfop-P-methyl, haloxyfop-sodium, HCH, hemel, hempa, HEOD,
heptachlor, heptenophos, heptopargil, heterophos,
hexachloroacetone, hexachlorobenzene, hexachlorobutadiene,
hexachlorophene, hexaconazole, hexaflumuron, hexaflurate, hexalure,
hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf,
huancaiwo, huangcaoling, huanjunzuo, hydramethylnon, hydrargaphen,
hydrated lime, hydrogen cyanide, hydroprene, hymexazol, hyquincarb,
IAA, IBA, icaridin, imazalil, imazalil nitrate, imazalil
sulfate,
imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium,
imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium,
imazaquin, imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium,
imazethapyr, imazethapyr-ammonium, imazosulfuron, imibenconazole,
imicyafos, imidacloprid, imidaclothiz, iminoctadine, iminoctadine
triacetate, iminoctadine trialbesilate, imiprothrin, inabenfide,
indanofan, indaziflam, indoxacarb, inezin, iodobonil, iodocarb,
iodomethane, iodosulfuron, iodosulfuron-methyl,
iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium,
ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium,
ipazine, ipconazole, ipfencarbazone, iprobenfos, iprodione,
iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, isamidofos,
isazofos, isobenzan, isocarbamid, isocarbophos, isocil, isodrin,
isofenphos, isofenphos-methyl, isolan, isomethiozin, isonoruron,
isopolinate, isoprocarb, isopropalin, isoprothiolane, isoproturon,
isopyrazam, isopyrimol, isothioate, isotianil, isouron,
isovaledione, isoxaben, isoxachlortole, isoxadifen,
isoxadifen-ethyl, isoxaflutole, isoxapyrifop, isoxathion,
ivermectin, izopamfos, japonilure, japothrins, jasmolin I, jasmolin
II, jasmonic acid, jiahuangchongzong, jiajizengxiaolin,
jiaxiangjunzhi, jiecaowan, jiecaoxi, jodfenphos, juvenile hormone
I, juvenile hormone II, juvenile hormone III, kadethrin,
karbutilate, karetazan, karetazan-potassium, kasugamycin,
kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox,
ketospiradox-potassium, kinetin, kinoprene, kresoxim-methyl,
kuicaoxi, lactofen, lambda-cyhalothrin, latilure, lead arsenate,
lenacil, lepimectin, leptophos, lindane, lineatin, linuron,
lirimfos, litlure, looplure, lufenuron, lvdingjunzhi, lvxiancaolin,
lythidathion, MAA, malathion, maleic hydrazide, malonoben,
maltodextrin, MAMA, mancopper, mancozeb, mandipropamid, maneb,
matrine, mazidox, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl,
MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl,
MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl,
MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl,
MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium,
mebenil, mecarbam, mecarbinzid, mecarphon, mecoprop,
mecoprop-2-ethylhexyl, mecoprop-dimethylammonium,
mecoprop-diolamine, mecoprop-ethadyl, mecoprop-isoctyl,
mecoprop-methyl, mecoprop-P, mecoprop-P-2-ethylhexyl,
mecoprop-P-dimethylammonium, mecoprop-P-isobutyl,
mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium,
mecoprop-trolamine, medimeform, medinoterb, medinoterb acetate,
medlure, mefenacet, mefenpyr, mefenpyr-diethyl, mefluidide,
mefluidide-diolamine, mefluidide-potassium, megatomoic acid,
menazon, mepanipyrim, meperfluthrin, mephenate, mephosfolan,
mepiquat, mepiquat chloride, mepiquat pentaborate, mepronil,
meptyldinocap, mercuric chloride, mercuric oxide, mercurous
chloride, merphos, mesoprazine, mesosulfuron, mesosulfuron-methyl,
mesotrione, mesulfen, mesulfenfos, metaflumizone, metalaxyl,
metalaxyl-M, metaldehyde, metam, metam-ammonium, metamifop,
metamitron, metam-potassium, metam-sodium, metazachlor,
metazosulfuron, metazoxolon, metconazole, metepa, metflurazon,
methabenzthiazuron, methacrifos, methalpropalin, methamidophos,
methasulfocarb, methazole, methfuroxam, methidathion,
methiobencarb, methiocarb, methiopyrisulfuron, methiotepa,
methiozolin, methiuron, methocrotophos, methometon, methomyl,
methoprene, methoprotryne, methoquin-butyl, methothrin,
methoxychlor, methoxyfenozide, methoxyphenone, methyl apholate,
methyl bromide, methyl eugenol, methyl iodide, methyl
isothiocyanate, methylacetophos, methylchloroform, methyldymron,
methylene chloride, methylmercury benzoate, methylmercury
dicyandiamide, methylmercury pentachlorophenoxide,
methylneodecanamide, metiram, metobenzuron, metobromuron,
metofluthrin, metolachlor, metolcarb, metominostrobin, metosulam,
metoxadiazone, metoxuron, metrafenone, metribuzin, metsulfovax,
metsulfuron, metsulfuron-methyl, mevinphos, mexacarbate, mieshuan,
milbemectin, milbemycin oxime, milneb, mipafox, mirex, MNAF,
moguchun, molinate, molosultap, monalide, monisouron,
monochloroacetic acid, monocrotophos, monolinuron, monosulfuron,
monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquat
dichloride, moroxydine, moroxydine hydrochloride, morphothion,
morzid, moxidectin, MSMA, muscalure, myclobutanil, myclozolin,
N-(ethylmercury)-p-toluenesulphonanilide, nabam, naftalofos, naled,
naphthalene, naphthaleneacetamide, naphthalic anhydride,
naphthoxyacetic acids, naproanilide, napropamide, naptalam,
naptalam-sodium, natamycin, neburon, niclosamide,
niclosamide-olamine, nicosulfuron, nicotine, nifluridide,
nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin,
nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene,
nitrothal-isopropyl, norbormide, norflurazon, nornicotine, noruron,
novaluron, noviflumuron, nuarimol, OCH, octachlorodipropyl ether,
octhilinone, ofurace, omethoate, orbencarb, orfralure,
ortho-dichlorobenzene, orthosulfamuron, oryctalure, orysastrobin,
oryzalin, osthol, ostramone, oxabetrinil, oxadiargyl, oxadiazon,
oxadixyl, oxamate, oxamyl, oxapyrazon, oxapyrazon-dimolamine,
oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxine-copper,
oxolinic acid, oxpoconazole, oxpoconazole fumarate, oxycarboxin,
oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyfluorfen,
oxymatrine, oxytetracycline, oxytetracycline hydrochloride,
paclobutrazol, paichongding, para-dichlorobenzene, parafluron,
paraquat, paraquat dichloride, paraquat dimetilsulfate, parathion,
parathion-methyl, parinol, pebulate, pefurazoate, pelargonic acid,
penconazole, pencycuron, pendimethalin, penflufen, penfluron,
penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad,
pentmethrin, pentoxazone, perfluidone, permethrin, pethoxamid,
phenamacril, phenazine oxide, phenisopham, phenkapton,
phenmedipham, phenmedipham-ethyl, phenobenzuron, phenothrin,
phenproxide, phenthoate, phenylmercuriurea, phenylmercury acetate,
phenylmercury chloride, phenylmercury derivative of pyrocatechol,
phenylmercury nitrate, phenylmercury salicylate, phorate,
phosacetim, phosalone, phosdiphen, phosfolan, phosfolan-methyl,
phosglycin, phosmet, phosnichlor, phosphamidon, phosphine,
phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide,
picloram, picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl,
picloram-olamine, picloram-potassium, picloram-triethylammonium,
picloram-tris(2-hydroxypropyl)ammonium, picolinafen, picoxystrobin,
pindone, pindone-sodium, pinoxaden, piperalin, piperonyl butoxide,
piperonyl cyclonene, piperophos, piproctanyl, piproctanyl bromide,
piprotal, pirimetaphos, pirimicarb, pirimioxyphos,
pirimiphos-ethyl, pirimiphos-methyl, plifenate, polycarbamate,
polyoxins, polyoxorim, polyoxorim-zinc, polythialan, potassium
arsenite, potassium azide, potassium cyanate, potassium
gibberellate, potassium naphthenate, potassium polysulfide,
potassium thiocyanate, potassium .alpha.-naphthaleneacetate,
pp'-DDT, prallethrin, precocene I, precocene II, precocene III,
pretilachlor, primidophos, primisulfuron, primisulfuron-methyl,
probenazole, prochloraz, prochloraz-manganese, proclonol,
procyazine, procymidone, prodiamine, profenofos, profluazol,
profluralin, profluthrin, profoxydim, proglinazine,
proglinazine-ethyl, prohexadione, prohexadione-calcium,
prohydrojasmon, promacyl, promecarb, prometon, prometryn, promurit,
propachlor, propamidine, propamidine dihydrochloride, propamocarb,
propamocarb hydrochloride, propanil, propaphos, propaquizafop,
propargite, proparthrin, propazine, propetamphos, propham,
propiconazole, propineb, propisochlor, propoxur, propoxycarbazone,
propoxycarbazone-sodium, propyl isome, propyrisulfuron,
propyzamide, proquinazid, prosuler, prosulfalin, prosulfocarb,
prosulfuron, prothidathion, prothiocarb, prothiocarb hydrochloride,
prothioconazole, prothiofos, prothoate, protrifenbute, proxan,
proxan-sodium, prynachlor, pydanon, pymetrozine, pyracarbolid,
pyraclofos, pyraclonil, pyraclostrobin, pyraflufen,
pyraflufen-ethyl, pyrafluprole, pyramat, pyrametostrobin,
pyraoxystrobin, pyrasulfotole, pyrazolynate, pyrazophos,
pyrazosulfuron, pyrazosulfuron-ethyl, pyrazothion, pyrazoxyfen,
pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins,
pyribambenz-isopropyl, pyribambenz-propyl, pyribencarb,
pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol,
pyridalyl, pyridaphenthion, pyridate, pyridinitril, pyrifenox,
pyrifluquinazon, pyriftalid, pyrimethanil, pyrimidifen,
pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrimitate,
pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxyfen,
pyrithiobac, pyrithiobac-sodium, pyrolan, pyroquilon,
pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur, quassia,
quinacetol, quinacetol sulfate, quinalphos, quinalphos-methyl,
quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine,
quinonamid, quinothion, quinoxyfen, quintiofos, quintozene,
quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl,
quizalofop-P-tefuryl, quwenzhi, quyingding, rabenzazole,
rafoxanide, rebemide, resmethrin, rhodethanil, rhodojaponin-III,
ribavirin, rimsulfuron, rotenone, ryania, saflufenacil, saijunmao,
saisentong, salicylanilide, sanguinarine, santonin, schradan,
scilliroside, sebuthylazine, secbumeton, sedaxane, selamectin,
semiamitraz, semiamitraz chloride, sesamex, sesamolin, sethoxydim,
shuangjiaancaolin, siduron, siglure, silafluofen, silatrane, silica
gel, silthiofam, simazine, simeconazole, simeton, simetryn,
sintofen, SMA, S-metolachlor, sodium arsenite, sodium azide, sodium
chlorate, sodium fluoride, sodium fluoroacetate, sodium
hexafluorosilicate, sodium naphthenate, sodium
orthophenylphenoxide, sodium pentachlorophenoxide, sodium
polysulfide, sodium thiocyanate, sodium .alpha.-naphthaleneacetate,
sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen,
spirotetramat, spiroxamine, streptomycin, streptomycin
sesquisulfate, strychnine, sulcatol, sulcofuron, sulcofuron-sodium,
sulcotrione, sulfallate, sulfentrazone, sulfiram, sulfluramid,
sulfometuron, sulfometuron-methyl, sulfosulfuron, sulfotep,
sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl
fluoride, sulglycapin, sulprofos, sultropen, swep, tau-fluvalinate,
tavron, tazimcarb, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl,
TCA-magnesium, TCA-sodium, TDE, tebuconazole, tebufenozide,
tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron,
tecloftalam, tecnazene, tecoram, teflubenzuron, tefluthrin,
tefuryltrione, tembotrione, temephos, tepa, TEPP, tepraloxydim,
terallethrin, terbacil, terbucarb, terbuchlor, terbufos,
terbumeton, terbuthylazine, terbutryn, tetcyclacis,
tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon,
tetrafluron, tetramethrin, tetramethylfluthrin, tetramine,
tetranactin, tetrasul, thallium sulfate, thenylchlor,
theta-cypermethrin, thiabendazole, thiacloprid, thiadifluor,
thiamethoxam, thiapronil, thiazafluron, thiazopyr, thicrofos,
thicyofen, thidiazimin, thidiazuron, thiencarbazone,
thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,
thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim,
thiocyclam, thiocyclam hydrochloride, thiocyclam oxalate,
thiodiazole-copper, thiodicarb, thiofanox, thiofluoximate,
thiohempa, thiomersal, thiometon, thionazin, thiophanate,
thiophanate-methyl, thioquinox, thiosemicarbazide, thiosultap,
thiosultap-diammonium, thiosultap-disodium, thiosultap-monosodium,
thiotepa, thiram, thuringiensin, tiadinil, tiaojiean, tiocarbazil,
tioclorim, tioxymid, tirpate, tolclofos-methyl, tolfenpyrad,
tolylfluanid, tolylmercury acetate, topramezone, tralkoxydim,
tralocythrin, tralomethrin, tralopyril, transfluthrin,
transpermethrin, tretamine, triacontanol, triadimefon, triadimenol,
triafamone, tri-allate, triamiphos, triapenthenol, triarathene,
triarimol, triasulfuron, triazamate, triazbutil, triaziflam,
triazophos, triazoxide, tribenuron, tribenuron-methyl, tribufos,
tributyltin oxide, tricamba, trichlamide, trichlorfon,
trichlormetaphos-3, trichloronat, triclopyr, triclopyr-butotyl,
triclopyr-ethyl, triclopyr-triethylammonium, tricyclazole,
tridemorph, tridiphane, trietazine, trifenmorph, trifenofos,
trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium,
triflumizole, triflumuron, trifluralin, triflusulfuron,
triflusulfuron-methyl, trifop, trifop-methyl, trifopsime,
triforine, trihydroxytriazine, trimedlure, trimethacarb,
trimeturon, trinexapac, trinexapac-ethyl, triprene, tripropindan,
triptolide, tritac, triticonazole, tritosulfuron, trunc-call,
uniconazole, uniconazole-P, urbacide, uredepa, valerate,
validamycin, valifenalate, valone, vamidothion, vangard,
vaniliprole, vernolate, vinclozolin, warfarin, warfarin-potassium,
warfarin-sodium, xiaochongliulin, xinjunan, xiwojunan, XMC,
xylachlor, xylenols, xylylcarb, yishijing, zarilamid, zeatin,
zengxiaoan, zeta-cypermethrin, zinc naphthenate, zinc phosphide,
zinc thiazole, zineb, ziram, zolaprofos, zoxamide, zuomihuanglong,
.alpha.-chlorohydrin, .alpha.-ecdysone, .alpha.-multistriatin, and
.alpha.-naphthaleneacetic acid.
14. The composition of claim 1, further comprising an
agriculturally acceptable carrier.
15. The composition of claim 1, wherein the compound is in the form
of a pesticidally acceptable acid addition salt.
16. The composition of claim 1, wherein the compound is in the form
of a salt derivative.
17. The composition of claim 1, wherein the compound is in the form
a hydrate.
18. The composition of claim 1, wherein the compound is a resolved
stereoisomer.
19. The composition of claim 1, wherein the compound is in the form
a crystal polymorph.
20. The composition of claim 1, wherein the compound comprises a
.sup.2H in place of .sup.1H.
21. The composition of claim 1, wherein the compound comprises a
.sup.13C in place of a .sup.12C.
22. The composition of claim 1, further comprising a
biopesticide.
23. The composition of claim 1, further comprising at least one of
the following compounds: (a)
3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-zaspiro[4,5]dec-3-en-2--
one; (b)
3-(4'-chloro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa-1--
azaspiro[4,5]dec-3-en-2-one; (c)
4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone; (d)
4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;
(e)
3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2-
,2-tetrafluoro-1-(trifluoromethypethyl]phenyl]-1,2-benzenedicarboxamide;
(f) 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide; (g)
2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; (h)
2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide; (i)
2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide; (j)
2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide; (k)
2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide; (l)
2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide; (m)
3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-
-carboxamide; (n)
N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-.alpha.,.alpha.,.alpha.--
trifluoro-p-tolyl)hydrazone; (o)
N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-.al-
pha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone nicotine; (p)
O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-
-methyl thiocarbonate; (q)
(E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;
(r)
1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-
-imidazo[1,2-a]pyridin-5-ol; (s)
4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate;
and (t)
N-ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro--
.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone.
24. The composition of claim 1, further comprising a compound
having one or more of the following modes of action:
acetylcholinesterase inhibitor; sodium channel modulator; chitin
biosynthesis inhibitor; GABA and glutamate-gated chloride channel
antagonist; GABA and glutamate-gated chloride channel agonist;
acetylcholine receptor agonist; acetylcholine receptor antagonist;
MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic
acetylcholine receptor; Midgut membrane disrupter; oxidative
phosphorylation disrupter, and ryanodine receptor (RyRs).
25. The composition of claim 1, further comprising a seed.
26. The composition of claim 1, further comprising a seed that has
been genetically modified to express one or more specialized
traits.
27. The composition of to claim 1, wherein the composition is
encapsulated inside, or placed on the surface of, a capsule.
28. The composition of claim 1, wherein the composition is
encapsulated inside, or placed on the surface of, a capsule,
wherein the capsule has a diameter of about 100-900 nanometers or
about 10-900 microns.
29. A process comprising applying a composition of claim 1, to an
area to control a pest, in an amount sufficient to control such
pest.
30. The process of claim 29, wherein the pest is selected from
beetles, earwigs, cockroaches, flies, aphids, scales, whiteflies,
leafhoppers, ants, wasps, termites, moths, butterflies, lice,
grasshoppers, locusts, crickets, fleas, thrips, bristletails,
mites, ticks, nematodes, and symphylans.
31. The process of claim 29, wherein the pest is from the Phyla
Nematoda or Arthropoda.
32. The process of claim 29, wherein the pest is from the Subphyla
Chelicerata, Myriapoda, or Hexapoda.
33. The process of claim 29, wherein the pest is from the Class of
Arachnida, Symphyla, or Insecta.
34. The process of claim 29, wherein the pest is from the Order
Anoplura, Order Coleoptera, Order Dermaptera, Order Blattaria,
Order Diptera, Order Hemiptera, Order Hymenoptera, Order Isoptera,
Order Lepidoptera, Order Mallophaga, Order Orthoptera, Order
Siphonaptera, Order Thysanoptera, Order Thysanura, Order Acarina,
or Order Symphyla.
35. The process of claim 29, wherein the pest is MYZUPE or
BEMITA.
36. The process of claim 29, wherein an amount of the composition
is from about 0.01 grams per hectare to about 5000 grams per
hectare.
37. The process of claim 29, wherein an amount of the composition
is from about 0.1 grams per hectare to about 500 grams per
hectare.
38. The process of claim 29, wherein an amount of the composition
is from about 1 gram per hectare to about 50 grams per hectare.
39. The process of claim 29, wherein the area is an area where
apples, corn, cotton, soybeans, canola, wheat, rice, sorghum,
barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries,
tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets,
or beans, are growing, or the seeds thereof are going to be
planted.
40. The process of claim 29, further comprising applying the
composition to a genetically modified plant that has been
genetically modified to express one or more specialized traits.
41. The process of claim 29, where the composition further
comprises ammonium sulfate.
42. A method of preparing the 1-(3-pyridyl-N-oxide)pyrazole
compound of claim 1, the method comprising: ##STR00269## oxidizing
a 1-(3-pyridyl)pyrazole compound of formula 1-1 to provide the
1-(3-pyridyl-N-oxide)pyrazole compound of formula 1-2, wherein
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.10, Q, and n are defined as in claim 1.
43. A method of preparing the 1-(3-pyridyl-N-oxide)pyrazole
compound of claim 1, the method comprising: ##STR00270## reacting
the 1-(3-pyridyl-N-oxide)pyrazole compound 2-3 with a carboxyl
compound of formula 3-1 where R.sub.12 is OH or Cl, to provide
1-(3-pyridyl-N-oxide)pyrazole-4-amide compound of formula 3-2.
44. The method of claim 43, further comprising: treating the
1-(3-pyridyl-N-oxide)pyrazole-4-amide compound of formula 3-2 with
a thionating agent to provide
1-(3-pyridyl-N-oxide)pyrazole-4-thioamide compound of formula 4-1
##STR00271##
45. A method of preparing the 1-(3-pyridyl-N-oxide)pyrazole
compound of claim 1, the method comprising: ##STR00272## oxidizing
a 1-(3-pyridyl-N-oxide)pyrazole sulfide of formula 5-1 to provide a
1-(3-pyridyl-N-oxide)pyrazole compound of formula 5-2, wherein
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.9, R.sub.10, Q, and n are defined as in claim 1.
Description
TECHNICAL FIELD
This disclosure relates to the field of compounds having pesticidal
utility against pests in Phyla Nematoda, Arthropoda, and/or
Mollusca, processes to produce such compounds and intermediates
used in such processes. These compounds may be used, for example,
as nematicides, acaricides, insecticides, miticides, and/or
molluscicides.
BACKGROUND
Controlling pest populations is essential to human health, modern
agriculture, food storage, and hygiene. There are more than ten
thousand species of pests that cause losses in agriculture and the
world-wide agricultural losses amount to billions of U.S. dollars
each year. Accordingly, there exists a continuous need for new
pesticides and for methods of producing and using such
pesticides.
DISCLOSURE
Definitions
The examples given in the definitions are non-exhaustive and must
not be construed as limiting the present disclosure. It is
understood that a substituent should comply with chemical bonding
rules and steric compatibility constraints in relation to the
particular molecule to which it is attached.
"Alkyl" means and includes an acyclic, saturated, branched or
unbranched hydrocarbon. Non-limiting examples may include methyl,
ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl,
pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl,
nonyl, or decyl.
"Cycloalkyl" means and includes a monocyclic or polycyclic
saturated hydrocarbon. Non-limiting examples may include
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, cyclodecyl, norbornyl, bicycle[2.2.2]octyl, or
decahydronapthyl.
"Alkenyl" means and includes an acyclic, branched or unbranched
hydrocarbon containing at least one carbon-carbon double bond.
Non-limiting examples may include ethenyl, propenyl, butenyl,
pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
"Cycloalkenyl" means and includes a monocyclic or polycyclic
hydrocarbon containing at least one carbon-carbon double bond.
Non-limiting examples may include cyclopentenyl, cyclohexenyl,
cycloheptenyl, cyclooctenyl, or cyclodecenyl.
"Alkynyl" means and includes acyclic, branched or unbranched
hydrocarbon containing at least one carbon-carbon triple bond.
Non-limiting examples may include ethynyl, propargyl, butynyl,
pentynyl, hexynyl, heptynyl, octynyl, nonynyl, or decynyl.
"Cycloalkynyl" means and includes a monocyclic or polycyclic
hydrocarbon containing at least one carbon-carbon triple bond.
Non-limiting examples may include cycloheptynyl, cyclooctynyl, or
cyclodecynyl.
"Aryl" means and includes an aromatic compound with or without any
substitution. Non-limiting examples may include phenyl or
naphthyl.
"Alkoxy" means and includes an alkyl group containing at least one
carbon-oxygen single bond. Non-limiting examples may include
methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, or
cyclopentoxy.
"Alkenyloxy" means and includes an alkenyl containing at least one
carbon-oxygen single bond. Non-limiting examples may include
allyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy,
octenyloxy, nonenyloxy, or decenyloxy.
"Alkynyloxy" means and includes an alkynyl containing at least one
carbon-oxygen single bond. Non-limiting examples may include
pentynyloxy, hexynyloxy, heptynyloxy, octynyloxy, nonynyloxy, or
decynyloxy.
"Cycloalkoxy" means and includes a cycloalkyl containing at least
one carbon-oxygen single bond. Non-limiting examples may include
cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,
cycloheptyloxy, cyclooctyloxy, cyclodecyloxy, norbornyloxy, or
bicyclo[2.2.2]octyloxy.
"Cyclohaloalkyl" means and includes a monocyclic or polycyclic,
saturated substituent comprising carbon, halogen, and hydrogen.
Non-limiting examples may include 1-chlorocyclopropyl,
1-chlorocyclobutyl, or 1-dichlorocyclopentyl.
"Cycloalkenyloxy" means and include a cycloalkenyl further
consisting of a carbon-oxygen single bond. Non-limiting examples
may include cyclobutenyloxy, cyclopentenyloxy, cyclohexenyloxy,
cycloheptenyloxy, cyclooctenyloxy, cyclodecenyloxy, norbornenyloxy,
or bicyclo[2.2.2] octenyloxy.
"Alkylthio" means and includes an alkyl group containing at least
one carbon-sulfur single bond.
"Haloalkylthio" means and includes an alkyl group containing at
least one carbon-sulfur single bond and halogen atom.
"Halo" or "halogen" means and includes fluorine, chlorine, bromine,
or iodine.
"Haloalkyl" means and includes an alkyl group substituted with at
least one halogen atom.
"Haloalkoxy" means and includes an alkoxy group substituted with at
least one halogen atom.
"Heteroatom" means and includes sulfur (S), oxygen (O), or nitrogen
(N) atom.
"Heteroalkyl" means and includes an alkyl containing at least one
sulfur (S), oxygen (O), or nitrogen (N) atom.
"Heterocyclyl" means a cyclic substituent that may be fully
saturated, partially unsaturated, or fully unsaturated, where the
cyclic structure contains at least one carbon and at least one
heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen.
In the case of sulfur, that atom can be in other oxidation states
such as a sulfoxide and sulfone. Examples of aromatic heterocyclyls
include, but are not limited to, benzofuranyl, benzoisothiazolyl,
benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl,
cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl,
isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl,
oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl,
pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl,
quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl,
thienyl, triazinyl, and triazolyl. Examples of fully saturated
heterocyclyls include, but are not limited to, piperazinyl,
piperidinyl, morpholinyl, pyrrolidinyl, oxetanyl,
tetrahydrofuranyl, tetrahydrothienyl and tetrahydropyranyl.
Examples of partially unsaturated heterocyclyls include, but are
not limited to, 1,2,3,4-tetrahydroquinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl. Additional examples include the
following
##STR00002##
"Pesticidally effective amount" means and includes an amount of
active material that causes an adverse effect to the at least one
insect, wherein the adverse effect may include deviations from
natural development, killing, regulation, or the like.
"Control" or grammatical variations thereof means and includes
regulating the number of living insects or regulating the number of
viable eggs of the insects, or both.
"Synergistic effect" or grammatical variations thereof means and
includes a cooperative action encountered in a combination of two
or more active agents in which the combined activity of the two or
more active agents exceeds the sum of the activity of each active
agent alone.
Pesticidal Compounds
In one particular embodiment, a pesticidal composition comprises at
least one compound selected from 1-(3-pyridyl-N-oxide)pyrazole
compound of formula I, II, or III, or any agriculturally acceptable
salt thereof:
##STR00003## wherein:
R.sub.1, R.sub.2, and R.sub.4 are independently selected from H, F,
Cl, Br, I, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, or
substituted or unsubstituted C.sub.1-C.sub.6 haloalkyl, wherein
each said R.sub.1, R.sub.2, and R.sub.4, when substituted, has one
or more substituents selected from F, Cl, Br, I, CN, NO.sub.2,
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.10 cycloalkyl, or C.sub.3-C.sub.10
halocycloalkyl, (each of which that can be substituted, may
optionally be substituted with R.sub.10);
R.sub.3, R.sub.12, and R.sub.13 are independently selected from H,
F, Cl, Br, I, CN, NO.sub.2, substituted or unsubstituted
C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6
alkenyl, substituted or unsubstituted C.sub.1-C.sub.6 alkoxy,
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl,
substituted or unsubstituted C.sub.1-C.sub.6 haloalkyl, substituted
or unsubstituted C.sub.6-C.sub.20 aryl, substituted or
unsubstituted C.sub.1-C.sub.20 heterocyclyl, OR.sub.11,
C(.dbd.X.sub.1)R.sub.11, C(.dbd.X.sub.1)OR.sub.11,
C(.dbd.X.sub.1)N(R.sub.11).sub.2, N(R.sub.11).sub.2,
N(R.sub.11)C(.dbd.X.sub.1)R.sub.11, SR.sub.11, S(O).sub.nOR.sub.11,
or R.sub.11S(O).sub.nR.sub.11, wherein each said R.sub.3, when
substituted, has one or more substituents selected from F, Cl, Br,
I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6 haloalkenyl,
C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6 haloalkenyloxy,
C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 cycloalkenyl,
C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10 halocycloalkenyl,
OR.sub.11, S(O).sub.nOR.sub.11, C.sub.6-C.sub.20 aryl, or
C.sub.1-C.sub.20 heterocyclyl, (each of which that can be
substituted, may optionally be substituted with R.sub.10);
R.sub.5 is H, F, Cl, Br, I, CN, NO.sub.2, substituted or
unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted
C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.10 cycloalkyl, substituted or
unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, OR.sub.11, C(.dbd.X.sub.1)R.sub.11,
C(.dbd.X.sub.1)OR.sub.11, C(.dbd.X.sub.1)N(R.sub.11).sub.2,
N(R.sub.11).sub.2, N(R.sub.11)C(.dbd.X.sub.1)R.sub.11, SR.sub.11,
S(O).sub.nOR.sub.11, or R.sub.11S(O).sub.nR.sub.11, wherein each
said R.sub.5, when substituted, has one or more substituents
selected from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10
halocycloalkenyl, OR.sub.11, S(O).sub.nOR.sub.11, C.sub.6-C.sub.20
aryl, or C.sub.1-C.sub.20 heterocyclyl, (each of which that can be
substituted, may optionally be substituted with R.sub.10);
R.sub.6 is H, F, Cl, Br, I, substituted or unsubstituted
C.sub.1-C.sub.6 alkyl, or C.sub.1-C.sub.6 haloalkyl, wherein each
said R.sub.6, when substituted, has one or more substituents
selected from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3-C.sub.10 halocycloalkyl, or C.sub.3-C.sub.10
halocycloalkenyl;
R.sub.7 is selected from H, substituted or unsubstituted
C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6
alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl,
substituted or unsubstituted C.sub.1-C.sub.6 alkoxy, substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkyl, substituted or
unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, C.sub.1-C.sub.6 alkyl
C.sub.6-C.sub.20 aryl wherein the alkyl and aryl is independently
substituted or unsubstituted, C.sub.1-C.sub.6
alkyl-(C.sub.3-C.sub.10 cyclohaloalkyl) wherein the alkyl and
cyclohaloalkyl is independently substituted or unsubstituted,
C.sub.1-C.sub.6 alkyl-(C.sub.3-C.sub.10 cycloalkyl) wherein the
alkyl and cycloalkyl is independently substituted or unsubstituted,
wherein each said R.sub.7, when substituted, has one or more
substituents selected from F, Cl, Br, I, CN, NO.sub.2,
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6
alkynyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6 haloalkenyl,
C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6 haloalkenyloxy,
C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 cycloalkenyl,
C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10 halocycloalkenyl,
OR.sub.11, S(O).sub.nOR.sub.11, C.sub.6-C.sub.20 aryl, or
C.sub.1-C.sub.20 heterocyclyl, or R.sub.11aryl, (each of which that
can be substituted, may optionally be substituted with
R.sub.10);
R.sub.8 is R.sub.9S(O).sub.nR.sub.10, or R.sub.9S(O).sub.nH;
R.sub.9 is substituted or unsubstituted C.sub.1-C.sub.12 alkyl,
substituted or unsubstituted C.sub.2-C.sub.12 alkenyl, or
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl,
wherein each said R.sub.9, when substituted, has one or more
substituents selected from F, Cl, Br, I, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 halocycloalkyl,
OR.sub.11, S(O).sub.nR.sub.11, C.sub.6-C.sub.20 aryl, or
C.sub.1-C.sub.20 heterocyclyl, (each of which that can be
substituted, may optionally be substituted with R.sub.10);
R.sub.10 is selected from substituted or unsubstituted
C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6
alkenyl, substituted or unsubstituted C.sub.1-C.sub.6 alkoxy,
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl,
substituted or unsubstituted C.sub.3-C.sub.10 halocycloalkyl
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl,
substituted or unsubstituted C.sub.6-C.sub.20 aryl, or substituted
or unsubstituted C.sub.1-C.sub.20 heterocyclyl, wherein each said
R.sub.10, when substituted, has one or more substituents selected
from F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6
haloalkenyl, C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6
haloalkenyloxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkenyl, C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10
halocycloalkenyl, oxo, OR.sub.11, S(O).sub.nR.sub.11,
C.sub.6-C.sub.20 aryl, or C.sub.1-C.sub.20 heterocyclyl, (each of
which that can be substituted, may optionally be substituted with
R.sub.10);
R.sub.11 is (each independently) selected from H, R.sub.8, CN,
substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or
unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted
C.sub.1-C.sub.6 alkoxy, substituted or unsubstituted
C.sub.2-C.sub.6 alkenyloxy, substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkyl, substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkenyl, substituted or unsubstituted
C.sub.6-C.sub.20 aryl, substituted or unsubstituted
C.sub.1-C.sub.20 heterocyclyl, substituted or unsubstituted
S(O).sub.nC.sub.1-C.sub.6 alkyl, or substituted or unsubstituted
N(C.sub.1-C.sub.6alkyl).sub.2, wherein each said R.sub.11, when
substituted, has one or more substituents selected from F, Cl, Br,
I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6 haloalkenyl,
C.sub.1-C.sub.6 haloalkyloxy, C.sub.2-C.sub.6 haloalkenyloxy,
C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 cycloalkenyl,
C.sub.3-C.sub.10 halocycloalkyl, C.sub.3-C.sub.10 halocycloalkenyl,
OC.sub.1-C.sub.6 alkyl, OC.sub.1-C.sub.6 haloalkyl,
S(O).sub.nC.sub.1-C.sub.6alkyl, S(O).sub.nOC.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.20 aryl, or C.sub.1-C.sub.20 heterocyclyl;
Y is a bond, or is substituted or unsubstituted C.sub.1-C.sub.6
alkyl, or substituted or unsubstituted C.sub.2-C.sub.6 alkenyl,
except where Y is a bond, wherein each said Y, when substituted,
has one or more substituents selected from F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6 haloalkenyl,
C.sub.1-C.sub.6 haloalkyloxy, or C.sub.3-C.sub.10 cycloalkyl,
Q is O or S;
X.sub.1 is (each independently) O or S; and
n is 0, 1, or 2.
In another embodiment, and in any combination with any of the
previous or following embodiments, R.sub.1, R.sub.2, and R.sub.4
are H.
In another embodiment, and in any combination with any of the
previous or following embodiments, R.sub.3 is selected from H, F,
Cl, Br, or I, preferably, H or F.
In another embodiment, and in any combination with any of the
previous or following embodiments, R.sub.5 is selected from F, Cl,
Br, I, or unsubstituted C.sub.1-C.sub.6 alkyl, preferably, Cl or
CH.sub.3.
In another embodiment, and in any combination with any of the
previous or following embodiments, R.sub.6 is H.
In another embodiment, and in any combination with any of the
previous or following embodiments, R.sub.7 is selected from H,
CH.sub.3, CH.sub.2CH.sub.3 CH.sub.2C.ident.CH, or
CH(CH.sub.3)C.ident.CH.
In another embodiment, and in any combination with any of the
previous or following embodiments, R.sub.8 is selected from
C.sub.1-C.sub.6 alkyl-S(O).sub.nCH.sub.2 (unsubstituted
C.sub.3-C.sub.10 halocycloalkyl), preferably, C.sub.1-C.sub.4
alkyl-S--CH.sub.2-halocyclopropyl, C.sub.1-C.sub.6
alkyl-S(O).sub.nC.sub.3-C.sub.6haloalkyl, preferably wherein said
halos are only on the carbon atom furthest from the sulfur atom,
such as CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CF.sub.3.
In another embodiment, and in any combination with any of the
previous or following embodiments, n is 0 or 1.
The 1-(3-pyridyl-N-oxide)pyrazole of formula I, when R.sub.7 is H,
may exist in various isomeric forms. Non-limiting examples of such
isomeric forms may include, but are not limited to, compounds IA or
IB as shown below.
##STR00004##
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole of formula
1-2 may be prepared as shown in Scheme 1.
##STR00005##
The 1-(3-pyridyl)pyrazole compound 1-1 (prepared as described in
the U.S. Publication No. 2012/0110702) may be treated with about
2.2 equivalents or more of an oxidant, such as sodium perborate
tetrahydrate, in a polar protic solvent, such as glacial acetic
acid (AcOH), at a temperature from about 0.degree. C. to about
80.degree. C. to give the 1-(3-pyridyl-N-oxide)pyrazole of formula
1-2, where n is 1 and/or 2. Alternatively, the
1-(3-pyridyl)pyrazole compound 1-1 may be oxidized with about three
or more equivalents of an oxidant, such as mCPBA, in an aprotic
solvent, such as dichloromethane (CH.sub.2Cl.sub.2), at a
temperature of from about -20.degree. C. to about 50.degree. C. to
give 1-(3-pyridyl-N-oxide)pyrazole compound of formula 1-2, where
n=2.
##STR00006##
In other embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound of
formula 2-3 may be prepared as shown in Scheme 2.
In step a of Scheme 2, the 1-(3-pyridyl)pyrazole compound 2-1
(prepared as described in the U.S. Publication No. 2012/0110702)
may be treated with an oxidant, such as mCPBA, in a solvent, such
as CH.sub.2Cl.sub.2, at a temperature of from about -20.degree. C.
to about 50.degree. C. to give the 1-(3-pyridyl-N-oxide)pyrazole of
formula 2-2.
In step b of Scheme 2, the Boc-protecting group of
1-(3-pyridyl-N-oxide)pyrazole 2-2 may be removed under conditions
known in the art, such as under acidic conditions using
trifluoroacetic acid (TFA), in a solvent, such as CH.sub.2Cl.sub.2,
to give 1-(3-pyridyl-N-oxide)pyrazole of formula 2-3.
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole-4-amide
compound of formula 3-2 may be prepared as shown in Scheme 3.
##STR00007##
The 1-(3-pyridyl-N-oxide)pyrazole-4-amine compound of formula 2-3
may be treated with a carboxyl compound of formula 3-1, where
R.sub.12 is either OH or Cl, to give the
1-(3-pyridyl-N-oxide)-4-amide compound of formula 3-2. When
R.sub.12 is OH, the 1-(3-pyridyl-N-oxide)pyrazole-4-amine 2-3 may
be converted to 1-(3-pyridyl-N-oxide)pyrazole-4-amide 3-2 in the
presence of a coupling reagent, such as
1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC),
and a base, such as N,N-dimethylaminopyridine (DMAP), in a polar
aprotic solvent, such as CH.sub.2Cl.sub.2. When R.sub.12 is Cl,
1-(3-pyridyl-N-oxide)pyrazole-4-amine 2-3 may be converted to
1-(3-pyridyl-N-oxide)pyrazole-4-amide 3-2 in the presence of a
base, such as diisopropylethylamine (DIPEA) and/or DMAP, and an
aprotic solvent, such as CH.sub.2Cl.sub.2 or N,N-dimethylformamide
(DMF).
##STR00008##
In other embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound of
formula 4-1 may be prepared as shown in Scheme 4. The
1-(3-pyridyl-N-oxide)pyrazole-4-amide of formula 3-2 may be treated
directly with a thionating agent (i.e., source of sulfur), such as
Lawesson's reagent, in an aprotic solvent, such as CH.sub.2Cl.sub.2
or toluene, under either conventional heating or microwave
irradiation at a temperature from about 60.degree. C. to about
150.degree. C. to provide 1-(3-pyridyl-N-oxide)pyrazole-4-thioamide
of formula 4-1.
##STR00009##
In further embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound
of formula 5-2 may be prepared as shown in Scheme 5. The
1-(3-pyridyl-N-oxide)pyrazole sulfide of formula 5-1 may be treated
with about one or more equivalents of an oxidant, such as sodium
perborate tetrahydrate, in a polar protic solvent, such as glacial
AcOH, to give 1-(3-pyridyl-N-oxide)pyrazole sulfoxide or
1-(3-pyridyl-N-oxide)pyrazole sulfone of formula 5-2, where n is 1
and/or 2, respectively. Alternatively, the
1-(3-pyridyl-N-oxide)pyrazole sulfide 5-1 may be treated with about
one or more equivalents of an oxidant, such as hydrogen peroxide
(H.sub.2O.sub.2), and a protic solvent, such as methanol (MeOH), to
give the corresponding sulfoxide or sulfone of formula 5-2, where n
is 1 and/or 2, respectively.
Pesticidally Acceptable Acid Addition Salts, Salt Derivatives,
Solvates, Ester Derivatives, Polymorphs, Isotopes, Radionuclides
and Stereoisomers
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound may
be formulated into pesticidally acceptable acid addition salts. By
way of a non-limiting example, an amine function can form salts
with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic,
benzoic, citric, malonic, salicylic, malic, fumaric, oxalic,
succinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic,
benzenesulfonic, methanesulfonic, ethanesulfonic,
hydroxymethanesulfonic, hydroxyethanesulfonic, and trifluoroacetic
acids. Additionally, by way of a non-limiting example, an acid
function can form salts including those derived from alkali or
alkaline earth metals and those derived from ammonia and amines.
Examples of preferred cations include sodium, potassium, and
magnesium.
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound may
be formulated into salt derivatives. By way of a non-limiting
example, a salt derivative can be prepared by contacting a free
base with a sufficient amount of the desired acid to produce a
salt. A free base may be regenerated by treating the salt with a
suitable dilute aqueous base solution such as dilute aqueous sodium
hydroxide (NaOH), potassium carbonate, ammonia, and sodium
bicarbonate. As an example, in many cases, a pesticide, such as
2,4-D, is made more water-soluble by converting it to its
dimethylamine salt.
In further embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound
may be formulated into stable complexes with a solvent, such that
the complex remains intact after the non-complexed solvent is
removed. These complexes are often referred to as "solvates."
However, it is particularly desirable to form stable hydrates with
water as the solvent.
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound may
be made into ester derivatives. These ester derivatives can then be
applied in the same manner as the invention disclosed in this
document is applied.
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound may
be made as various crystal polymorphs. Polymorphism is important in
the development of agrochemicals since different crystal polymorphs
or structures of the same molecule can have vastly different
physical properties and biological performances.
In further embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound
may be made with different isotopes. Of particular importance are
molecules having .sup.2H (also known as deuterium) in place of
.sup.1H.
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound may
be made with different radionuclides. Of particular importance are
molecules having .sup.13C or .sup.14C.
In some embodiments, the 1-(3-pyridyl-N-oxide)pyrazole compound may
exist as one or more stereoisomers. Thus, certain molecules can be
produced as racemic mixtures. It will be appreciated by those
skilled in the art that one stereoisomer may be more active than
the other stereoisomers. Individual stereoisomers may be obtained
by known selective synthetic procedures, by conventional synthetic
procedures using resolved starting materials, or by conventional
resolution procedures. Certain molecules disclosed in this document
can exist as two or more isomers. The various isomers include
geometric isomers, diastereomers, and enantiomers. Thus, the
molecules disclosed in this document include geometric isomers,
racemic mixtures, individual stereoisomers, and optically active
mixtures. It will be appreciated by those skilled in the art that
one isomer may be more active than the others. The structures
disclosed in the present disclosure are drawn in only one geometric
form for clarity, but are intended to represent all geometric forms
of the molecule.
Pesticidal Compositions
In one particular embodiment, a pesticidal composition comprises at
least one compound selected from 1-(3-pyridyl-N-oxide)pyrazole
compound of formula I, II, or III, or any agriculturally acceptable
salt thereof.
In some embodiments, a pesticidal composition comprises at least
one of a 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II,
or III, or any agriculturally acceptable salt thereof, and a
phytologically-acceptable inert carrier (e.g., solid carrier, or
liquid carrier).
In one embodiment, the pesticidal composition may further comprise
at least one additive selected from surfactant, a stabilizer, an
emetic agent, a disintegrating agent, an antifoaming agent, a
wetting agent, a dispersing agent, a binding agent, dyes, or
fillers.
In some embodiments, the pesticidal compositions may be in the form
of solid. Non-limiting examples of the solid forms may include
power, dust or granular formulations.
In other embodiments, the pesticidal compositions may be in the
form of liquid formulation. Examples of the liquid forms may
include, but not limited to, dispersion, suspension, emulsion or
solution in appropriate liquid carrier.
In further embodiments, the pesticidal compositions may be in the
form of liquid dispersion, wherein the
1-(3-pyridyl-N-oxide)pyrazole compound may be dispersed in water or
other agriculturally suitable liquid carrier.
In yet further embodiments, the pesticidal compositions may be in
the form of solution in an appropriate organic solvent. In one
embodiment, the spray oils, which are widely used in agricultural
chemistry, may be used as an organic solvent for the pesticidal
compositions.
The pesticidal composition may be used in conjunction (such as, in
a compositional mixture, or a simultaneous or sequential
application) with one or more compounds having acaricidal,
algicidal, avicidal, bactericidal, fungicidal, herbicidal,
insecticidal, molluscicidal, nematicidal, rodenticidal, and/or
virucidal properties.
Furthermore, the pesticidal composition may be used in conjunction
(such as, in a compositional mixture, or a simultaneous or
sequential application) with one or more compounds that are
antifeedants, bird repellents, chemosterilants, herbicide safeners,
insect attractants, insect repellents, mammal repellents, mating
disrupters, plant activators, plant growth regulators, and/or
synergists.
Insecticides
Non-limiting examples of insecticides that may be used in
combination with the 1-(3-pyridyl-N-oxide)pyrazole compound of
formula I, II, or III may include 1,2-dichloropropane, abamectin,
acephate, acetamiprid, acethion, acetoprole, acrinathrin,
acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin,
allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone,
ct/p/w-endosulfan, amidithion, aminocarb, amiton, amiton oxalate,
amitraz, anabasine, athidathion, azadirachtin, azamethiphos,
azinphos-ethyl, azinphos-methyl, azothoate, barium
hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap,
beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin,
bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid,
bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl,
bufencarb, buprofezin, butacarb, butathiofos, butocarboxim,
butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium
polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon
disulfide, carbon tetrachloride, carbophenothion, carbosulfan,
cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen,
chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride,
chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,
chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos,
chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide,
cinerin I, cinerin II, cinerins, cismethrin, cloethocarb,
closantel, clothianidin, copper acetoarsenite, copper arsenate,
copper naphthenate, copper oleate, coumaphos, coumithoate,
crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos,
cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin,
cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine,
cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O,
demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl,
demeton-S, demeton-S-methyl, demeton-S-methylsulphon,
diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,
dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil,
dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan,
dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex,
dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan,
dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos,
d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,
doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC,
empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,
eprinomectin, esdepallethrine, esfenvalerate, etaphos,
ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl
formate, ethyl-DDD, ethylene dibromide, ethylene dichloride,
ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos,
fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion,
fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin,
fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil,
flonicamid, flubendiamide (additionally resolved isomers thereof),
flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron,
flufenprox, fluvalinate, fonofos, formetanate, formetanate
hydrochloride, formothion, formparanate, formparanate
hydrochloride, fosmethilan, fospirate, fosthietan, fufenozide,
furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox,
halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos,
hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene,
hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane,
IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos,
isofenphos-methyl, isoprocarb, isoprothiolane, isothioate,
isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos,
juvenile hormone I, juvenile hormone II, juvenile hormone III,
kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin,
leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion,
malonoben, mazidox, mecarbam, mecarphon, menazon, meperfluthrin,
mephosfolan, mercurous chloride, mesulfenfos, metaflumizone,
methacrifos, methamidophos, methidathion, methiocarb,
methocrotophos, methomyl, methoprene, methothrin, methoxychlor,
methoxyfenozide, methyl bromide, methyl isothiocyanate,
methylchloroform, methylene chloride, metofluthrin, metolcarb,
metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin
oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo,
monosultap, morphothion, moxidectin, naftalofos, naled,
naphthalene, nicotine, nifluridide, nitenpyram, nithiazine,
nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,
oxydemeton-methyl, oxydeprofos, oxydisulfoton,
para-dichlorobenzene, parathion, parathion-methyl, penfluron,
pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate,
phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon,
phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb,
pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium
thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II,
precocene III, primidophos, profenofos, profluralin, profluthrin,
promacyl, promecarb, propaphos, propetamphos, propoxur,
prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,
pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,
pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,
pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,
quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,
resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,
silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium
hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram,
spinosad, spiromesifen, spirotetramat, sulcofuron,
sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl
fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide,
tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos,
TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos,
tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid,
thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam
oxalate, thiodicarb, thiofanox, thiometon, thiosultap,
thiosultap-disodium, thiosultap-monosodium, thuringiensin,
tolfenpyrad, tralomethrin, transfluthrin, transpermethrin,
triarathene, triazamate, triazophos, trichlorfon,
trichlormetaphos-3, trichloronat, trifenofos, triflumuron,
trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb,
zeta-cypermethrin, or zolaprofos.
Acaricides
Non-limiting examples of acaricides that may be used in combination
with the 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II,
or III may include acequinocyl, amidoflumet, arsenous oxide,
azobenzene, azocyclotin, benomyl, benoxafos, benzoximate, benzyl
benzoate, bifenazate, binapacryl, bromopropylate, chinomethionat,
chlorbenside, chlorfenethol, chlorfenson, chlorfensulphide,
chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate,
clofentezine, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid,
dicofol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4,
dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenyl
sulfone, disulfiram, dofenapyn, etoxazole, fenazaquin, fenbutatin
oxide, fenothiocarb, fenpyroximate, fenson, fentrifanil,
fluacrypyrim, fluazuron, flubenzimine, fluenetil, flumethrin,
fluorbenside, hexythiazox, mesulfen, MNAF, nikkomycins, proclonol,
propargite, quintiofos, spirodiclofen, sulfiram, sulfur,
tetradifon, tetranactin, tetrasul, or thioquinox.
Nematicides
Non-limiting examples of nematicides that may be used in
combination with the 1-(3-pyridyl-N-oxide)pyrazole compound of
formula I, II, or III may include 1,3-dichloropropene, benclothiaz,
dazomet, dazomet-sodium, DBCP, DCIP, diamidafos, fluensulfone,
fosthiazate, furfural, imicyafos, isamidofos, isazofos, metam,
metam-ammonium, metam-potassium, metam-sodium, phosphocarb, or
thionazin.
Fungicides
Non-limiting examples of fungicides that may be used in combination
with the 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II,
or III may include (3-ethoxypropyl)mercury bromide,
2-methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinoline
sulfate, 8-phenylmercurioxyquinoline, acibenzolar,
acibenzolar-S-methyl, acypetacs, acypetacs-copper, acypetacs-zinc,
aldimorph, allyl alcohol, ametoctradin, amisulbrom, ampropylfos,
anilazine, aureofungin, azaconazole, azithiram, azoxystrobin,
barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl,
benquinox, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl,
benzalkonium chloride, benzamacril, benzamacril-isobutyl,
benzamorf, benzohydroxamic acid, bethoxazin, binapacryl, biphenyl,
bitertanol, bithionol, bixafen, blasticidin-S, Bordeaux mixture,
boscalid, bromuconazole, bupirimate, Burgundy mixture, buthiobate,
butylamine, calcium polysulfide, captafol, captan, carbamorph,
carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture,
chinomethionat, chlobenthiazone, chloraniformethan, chloranil,
chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin,
chlorothalonil, chlorquinox, chlozolinate, climbazole,
clotrimazole, copper acetate, copper carbonate, basic, copper
hydroxide, copper naphthenate, copper oleate, copper oxychloride,
copper silicate, copper sulfate, copper zinc chromate, cresol,
cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid,
cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole,
cyprodinil, dazomet, dazomet-sodium, DBCP, debacarb, decafentin,
dehydroacetic acid, dichlofluanid, dichlone, dichlorophen,
dichlozoline, diclobutrazol, diclocymet, diclomezine,
diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate,
difenoconazole, diflumetorim, dimethirimol, dimethomorph,
dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap,
dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon,
diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon,
DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph,
dodemorph acetate, dodemorph benzoate, dodicin, dodicin-sodium,
dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etem,
ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl
mercaptide, ethylmercury acetate, ethylmercury bromide,
ethylmercury chloride, ethylmercury phosphate, etridiazole,
famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol,
fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil,
fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin chloride,
fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,
flumetover, flumorph, fluopicolide, fluopyram, fluoroimide,
fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,
flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad,
folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole,
furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis,
furfural, furmecyclox, furophanate, glyodin, griseofulvin,
guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene,
hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil,
imazalil nitrate, imazalil sulfate, imibenconazole, iminoctadine,
iminoctadine triacetate, iminoctadine trialbesilate, iodomethane,
ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane,
isopyrazam, isotianil, isovaledione, kasugamycin, kresoxim-methyl,
mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid,
mepanipyrim, mepronil, meptyldinocap, mercuric chloride, mercuric
oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,
metam-ammonium, metam-potassium, metam-sodium, metazoxolon,
metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl
isothiocyanate, methylmercury benzoate, methylmercury
dicyandiamide, methylmercury pentachlorophenoxide, metiram,
metominostrobin, metrafenone, metsulfovax, milneb, myclobutanil,
myclozolin, N-(ethylmercury)-p-toluenesulphonanilide, nabam,
natamycin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH,
octhilinone, ofurace, orysastrobin, oxadixyl, oxine-copper,
oxpoconazole, oxpoconazole fumarate, oxycarboxin, pefurazoate,
penconazole, pencycuron, penflufen, pentachlorophenol,
penthiopyrad, phenylmercuriurea, phenylmercury acetate,
phenylmercury chloride, phenylmercury derivative of pyrocatechol,
phenylmercury nitrate, phenylmercury salicylate, phosdiphen,
phthalide, picoxystrobin, piperalin, polycarbamate, polyoxins,
polyoxorim, polyoxorim-zinc, potassium azide, potassium
polysulfide, potassium thiocyanate, probenazole, prochloraz,
procymidone, propamocarb, propamocarb hydrochloride, propiconazole,
propineb, proquinazid, prothiocarb, prothiocarb hydrochloride,
prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin,
pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb,
pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon,
pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid,
quinconazole, quinoxyfen, quintozene, rabenzazole, salicylanilide,
sedaxane, silthiofam, simeconazole, sodium azide, sodium
orthophenylphenoxide, sodium pentachlorophenoxide, sodium
polysulfide, spiroxamine, streptomycin, sulfur, sultropen, TCMTB,
tebuconazole, tebufloquin, tecloftalam, tecnazene, tecoram,
tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide,
thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl,
thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl,
tolylfluanid, tolylmercury acetate, triadimefon, triadimenol,
triamiphos, triarimol, triazbutil, triazoxide, tributyltin oxide,
trichlamide, tricyclazole, tridemorph, trifloxystrobin,
triflumizole, triforine, triticonazole, uniconazole, uniconazole-P,
validamycin, valifenalate, vinclozolin, zarilamid, zinc
naphthenate, zineb, ziram, or zoxamide.
Herbicides
Non-limiting examples of herbicides that may be used in combination
the 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may include 2,3,6-TBA, 2,3,6-TBA-dimethylammonium,
2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl,
2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB,
2,4,5-T-butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl,
2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,
2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,
2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,
2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,
2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,
2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,
2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,
2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP,
2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl,
2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium,
2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl,
2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl,
2,4-D-tetradecylammonium, 2,4-D-triethylammonium,
2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA,
3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen,
acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein,
alachlor, allidochlor, alloxydim, alloxydim-sodium, allyl alcohol,
alorac, ametridione, ametryn, amibuzin, amicarbazone,
amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl,
aminocyclopyrachlor-potassium, aminopyralid,
aminopyralid-potassium, aminopyralid-tris(2-hydroxypropyl)ammonium,
amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron,
asulam, asulam-potassium, asulam-sodium, atraton, atrazine,
azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid,
benazolin, benazolin-dimethylammonium, benazolin-ethyl,
benazolin-potassium, bencarbazone, benfluralin, benfuresate,
bensulfuron, bensulfuron-methyl, bensulide, bentazone,
bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone,
benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop,
benzoylprop-ethyl, benzthiazuron, bicyclopyrone, bifenox,
bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, borax,
bromacil, bromacil-lithium, bromacil-sodium, bromobonil,
bromobutide, bromofenoxim, bromoxynil, bromoxynil butyrate,
bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium,
brompyrazon, butachlor, butafenacil, butamifos, butenachlor,
buthidazole, buthiuron, butralin, butroxydim, buturon, butylate,
cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide,
cambendichlor, carbasulam, carbetamide, carboxazole, carfentrazone,
carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben,
chloramben-ammonium, chloramben-diolamine, chloramben-methyl,
chloramben-methylammonium, chloramben-sodium, chloranocryl,
chlorazifop, chlorazifop-propargyl, chlorazine, chlorbromuron,
chlorbufam, chloreturon, chlorfenac, chlorfenac-sodium,
chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol,
chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,
chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil,
chlorprocarb, chlorpropham, chlorsulfuron, chlorthal,
chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid,
cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim,
cliodinate, clodinafop, clodinafop-propargyl, clofop,
clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim,
clopyralid, clopyralid-methyl, clopyralid-olamine,
clopyralid-potassium, clopyralid-tris(2-hydroxypropyl)ammonium,
cloransulam, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC,
credazine, cresol, cumyluron, cyanamide, cyanatryn, cyanazine,
cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop,
cyhalofop-butyl, cyperquat, cyperquat chloride, cyprazine,
cyprazole, cypromid, daimuron, dalapon, dalapon-calcium,
dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium,
delachlor, desmedipham, desmetryn, di-allate, dicamba,
dicamba-dimethylammonium, dicamba-diolamine,
dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine,
dicamba-potassium, dicamba-sodium, dicamba-trolamine, dichlobenil,
dichloralurea, dichlormate, dichlorprop, dichlorprop-2-ethylhexyl,
dichlorprop-butotyl, dichlorprop-dimethylammonium,
dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl,
dichlorprop-P, dichlorprop-P-dimethylammonium,
dichlorprop-potassium, dichlorprop-sodium, diclofop,
diclofop-methyl, diclosulam, diethamquat, diethamquat dichloride,
diethatyl, diethatyl-ethyl, difenopenten, difenopenten-ethyl,
difenoxuron, difenzoquat, difenzoquat metilsulfate, diflufenican,
diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate,
dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,
dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,
dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine,
dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate,
diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat
dibromide, disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC,
DNOC-ammonium, DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine,
eglinazine-ethyl, endothal, endothal-diammonium,
endothal-dipotassium, endothal-disodium, epronaz, EPTC, erbon,
esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl,
ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxyfen-ethyl,
ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam,
fenoprop, fenoprop-3-butoxypropyl, fenoprop-butometyl,
fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl,
fenoprop-methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl,
fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenteracol,
fenthiaprop, fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA,
ferrous sulfate, flamprop, flamprop-isopropyl, flamprop-M,
flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl,
flazasulfuron, florasulam, fluazifop, fluazifop-butyl,
fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, fluazolate,
flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin,
flufenacet, flufenican, flufenpyr, flufenpyr-ethyl, flumetsulam,
flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin,
flumipropyn, fluometuron, fluorodifen, fluoroglycofen,
fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron,
flupoxam, flupropacil, flupropanate, flupropanate-sodium,
flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone,
flurochloridone, fluroxypyr, fluroxypyr-butometyl,
fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl,
fomesafen, fomesafen-sodium, foramsulfuron, fosamine,
fosamine-ammonium, furyloxyfen, glufosinate, glufosinate-ammonium,
glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium,
glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium,
glyphosate-isopropylammonium, glyphosate-monoammonium,
glyphosate-potassium, glyphosate-sesquisodium,
glyphosate-trimesium, halosafen, halosulfuron, halosulfuron-methyl,
haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl,
haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl,
haloxyfop-sodium, hexachloroacetone, hexaflurate, hexazinone,
imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium,
imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium,
imazaquin, imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium,
imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan,
indaziflam, iodobonil, iodomethane, iodosulfuron,
iodosulfuron-methyl-sodium, ioxynil, ioxynil octanoate,
ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone,
iprymidam, isocarbamid, isocil, isomethiozin, isonoruron,
isopolinate, isopropalin, isoproturon, isouron, isoxaben,
isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate,
ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA,
MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium,
MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl,
MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-potassium,
MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl,
MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl,
mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,
mecoprop-isoctyl, mecoprop-methyl, mecoprop-P,
mecoprop-P-dimethylammonium, mecoprop-P-isobutyl,
mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium,
mecoprop-trolamine, medinoterb, medinoterb acetate, mefenacet,
mefluidide, mefluidide-diolamine, mefluidide-potassium,
mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, metam,
metam-ammonium, metamifop, metamitron, metam-potassium,
metam-sodium, metazachlor, metazosulfuron, metflurazon,
methabenzthiazuron, methalpropalin, methazole, methiobencarb,
methiozolin, methiuron, methometon, methoprotryne, methyl bromide,
methyl isothiocyanate, methyldymron, metobenzuron, metolachlor,
metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl,
molinate, monalide, monisouron, monochloroacetic acid, monolinuron,
monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA,
naproanilide, napropamide, naptalam, naptalam-sodium, neburon,
nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,
norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,
orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,
oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron,
oxaziclomefone, oxyfluorfen, parafluron, paraquat, paraquat
dichloride, paraquat dimetilsulfate, pebulate, pelargonic acid,
pendimethalin, penoxsulam, pentachlorophenol, pentanochlor,
pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham,
phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram,
picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl,
picloram-olamine, picloram-potassium, picloram-triethylammonium,
picloram-tris(2-hydroxypropyl)ammonium, picolinafen, pinoxaden,
piperophos, potassium arsenite, potassium azide, potassium cyanate,
pretilachlor, primisulfuron, primisulfuron-methyl, procyazine,
prodiamine, profluazol, profluralin, profoxydim, proglinazine,
proglinazine-ethyl, prometon, prometryn, propachlor, propanil,
propaquizafop, propazine, propham, propisochlor, propoxycarbazone,
propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin,
prosulfocarb, prosulfuron, proxan, proxan-sodium, prynachlor,
pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole,
pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen,
pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate,
pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan,
pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam,
quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop,
quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl,
quizalofop-P-tefuryl, rhodethanil, rimsulfuron, saflufenacil,
sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton,
simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide, sodium
chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron,
sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin,
swep, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium,
TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione,
tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,
terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron,
thiazopyr, thidiazimin, thidiazuron, thiencarbazone,
thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,
thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim,
tri-allate, triasulfuron, triaziflam, tribenuron,
tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl,
triclopyr-ethyl, triclopyr-triethylammonium, tridiphane,
trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin,
triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl,
trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,
tritosulfuron, vernolate, or xylachlor.
Biopesticides
The 1-(3-pyridyl-N-oxide)pyrazole compound may also be used in
combination (such as in a compositional mixture, or a simultaneous
or sequential application) with one or more biopesticides. The term
"biopesticide" is used for microbial biological pest control agents
that are applied in a similar manner to chemical pesticides.
Commonly these are bacterial, but there are also examples of fungal
control agents, including Trichoderma spp. and Ampelomyces
quisqualis (a control agent for grape powdery mildew). Bacillus
subtilis are used to control plant pathogens. Weeds and rodents
have also been controlled with microbial agents. One well-known
insecticide example is Bacillus thuringiensis, a bacterial disease
of Lepidoptera, Coleoptera, and Diptera. Because it has little
effect on other organisms, it is considered more environmentally
friendly than synthetic pesticides. Biological insecticides include
products based on: 1. entomopathogenic fungi (e.g. Metarhizium
anisopliae); 2. entomopathogenic nematodes (e.g. Steinernema
feltiae); and 3. entomopathogenic viruses (e.g. Cydia pomonella
granulovirus).
Other examples of entomopathogenic organisms include, but are not
limited to, baculoviruses, bacteria and other prokaryotic
organisms, fungi, protozoa and Microsproridia. Biologically derived
insecticides include, but not limited to, rotenone, veratridine, as
well as microbial toxins; insect tolerant or resistant plant
varieties; and organisms modified by recombinant DNA technology to
either produce insecticides or to convey an insect resistant
property to the genetically modified organism. In one embodiment,
the molecules of Formula One may be used with one or more
biopesticides in the area of seed treatments and soil amendments.
The Manual of Biocontrol Agents gives a review of the available
biological insecticide (and other biology-based control) products.
Copping L. G. (ed.) (2004). The Manual of Biocontrol Agents
(formerly the Biopesticide Manual) 3rd Edition. British Crop
Production Council (BCPC), Farnham, Surrey UK.
Other Active Compounds
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may also be used in combination (such as in a compositional
mixture, or a simultaneous or sequential application) with one or
more of the following: 1.
3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-e-2--
one; 2.
3-(4'-chloro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-a-
zaspiro[4,5]dec-3-en-2-one; 3.
4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone; 4.
4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;
5.
3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2-
,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;
6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide; 7.
2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; 8.
2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide; 9.
2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide; 10.
2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide; 11.
2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide; 12.
2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide; 13.
3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-
-carboxamide; 14.
N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-.alpha.,.alpha.,.alpha.--
trifluoro-p-tolyl) hydrazone; 15.
N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-.al-
pha.,.alpha.,.alpha.-trifluoro-p-tolyl) hydrazone nicotine; 16.
O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-
-methyl thiocarbonate; 17.
(E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;
18.
1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-
-imidazo[1,2-a]pyridin-5-ol; 19.
4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate;
and 20.
N-ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro--
.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)hydrazone.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may also be used in combination (such as in a compositional
mixture, or a simultaneous or sequential application) with one or
more compounds in the following groups: algicides, antifeedants,
avicides, bactericides, bird repellents, chemosterilants, herbicide
safeners, insect attractants, insect repellents, mammal repellents,
mating disrupters, molluscicides, plant activators, plant growth
regulators, rodenticides, or virucides.
Synergistic Mixtures and Synergists
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may be used in combination with at least one other insecticides to
form a synergistic mixture where the mode of action of such
compounds compared to the mode of action of the
1-(3-pyridyl-N-oxide)pyrazole compound are the same, similar, or
different. Examples of modes of action may include, but are not
limited to: acetylcholinesterase inhibitor; sodium channel
modulator; chitin biosynthesis inhibitor; GABA-gated chloride
channel antagonist; GABA and glutamate-gated chloride channel
agonist; acetylcholine receptor agonist; MET I inhibitor;
Mg-stimulated ATPase inhibitor; nicotinic acetylcholine receptor;
Midgut membrane disrupter; oxidative phosphorylation disrupter, or
ryanodine receptor (RyRs).
Additionally, the 1-(3-pyridyl-N-oxide)pyrazole compound of formula
I, II, or III may be used in combination with at least one of
fungicides, acaricides, herbicides or nematicides to form a
synergistic mixture.
Furthermore, the 1-(3-pyridyl-N-oxide)pyrazole compound of formula
I, II, or III may be used in combination with other active
compounds, such as the compounds under the heading "OTHER ACTIVE
COMPOUNDS," algicides, avicides, bactericides, molluscicides,
rodenticides, virucides, herbicide safeners, adjuvants, and/or
surfactants to form a synergistic mixture. Moreover, the following
compounds are known as synergists and may be used in combination
with the 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II,
or III: piperonyl butoxide, piprotal, propyl isome, sesamex,
sesamolin, sulfoxide, and tribufos.
Formulations
A pesticide is rarely suitable for application in its pure form. It
is usually necessary to add other substances so that the pesticide
can be used at the required concentration and in an appropriate
form, permitting ease of application, handling, transportation,
storage, and maximum pesticide activity. Thus, pesticides are
formulated into, for example, baits, concentrated emulsions, dusts,
emulsifiable concentrates, fumigants, gels, granules,
microencapsulations, seed treatments, suspension concentrates,
suspoemulsions, tablets, water soluble liquids, water dispersible
granules or dry flowables, wettable powders, and ultra low volume
solutions. For further information on formulation types see
"Catalogue of Pesticide Formulation Types and International Coding
System" Technical Monograph no. 2, 5th Edition by CropLife
International (2002).
Pesticides are applied most often as aqueous suspensions or
emulsions prepared from concentrated formulations of such
pesticides. Such water-soluble, water-suspendable, or emulsifiable
formulations are either solids, usually known as wettable powders,
or water dispersible granules, or liquids usually known as
emulsifiable concentrates, or aqueous suspensions. Wettable
powders, which may be compacted to form water dispersible granules,
comprise an intimate mixture of the pesticide, a carrier, and
surfactants. The concentration of the pesticide is usually from
about 10% to about 90% by weight. The carrier is usually selected
from among the attapulgite clays, the montmorillonite clays, the
diatomaceous earths, or the purified silicates. Effective
surfactants, comprising from about 0.5% to about 10% of the
wettable powder, are found among sulfonated lignins, condensed
naphthalenesulfonates, naphthalenesulfonates,
alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants
such as ethylene oxide adducts of alkyl phenols.
Emulsifiable concentrates of pesticides comprise a convenient
concentration of a pesticide, such as from about 50 to about 500
grams per liter of liquid dissolved in a carrier that is either a
water miscible solvent or a mixture of water-immiscible organic
solvent and emulsifiers. Useful organic solvents include aromatics,
especially xylenes and petroleum fractions, especially the
high-boiling naphthalenic and olefinic portions of petroleum such
as heavy aromatic naphtha. Other organic solvents may also be used,
such as the terpenic solvents including rosin derivatives,
aliphatic ketones such as cyclohexanone, and complex alcohols such
as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable
concentrates are selected from conventional anionic and non-ionic
surfactants.
Aqueous suspensions comprise suspensions of water-insoluble
pesticides dispersed in an aqueous carrier at a concentration in
the range from about 5% to about 50% by weight. Suspensions are
prepared by finely grinding the pesticide and vigorously mixing it
into a carrier comprised of water and surfactants. Ingredients,
such as inorganic salts and synthetic or natural gums may also be
added, to increase the density and viscosity of the aqueous
carrier. It is often most effective to grind and mix the pesticide
at the same time by preparing the aqueous mixture and homogenizing
it in an implement such as a sand mill, ball mill, or piston-type
homogenizer.
Pesticides may also be applied as granular compositions that are
particularly useful for applications to the soil. Granular
compositions usually contain from about 0.5% to about 10% by weight
of the pesticide, dispersed in a carrier that comprises clay or a
similar substance. Such compositions are usually prepared by
dissolving the pesticide in a suitable solvent and applying it to a
granular carrier which has been pre-formed to the appropriate
particle size, in the range of from about 0.5 to about 3 mm. Such
compositions may also be formulated by making a dough or paste of
the carrier and compound and crushing and drying to obtain the
desired granular particle size.
Dusts containing a pesticide are prepared by intimately mixing the
pesticide in powdered form with a suitable dusty agricultural
carrier, such as kaolin clay, ground volcanic rock, and the like.
Dusts can suitably contain from about 1% to about 10% of the
pesticide. They can be applied as a seed dressing or as a foliage
application with a dust blower machine.
It is equally practical to apply a pesticide in the form of a
solution in an appropriate organic solvent, usually petroleum oil,
such as the spray oils, which are widely used in agricultural
chemistry.
Pesticides can also be applied in the form of an aerosol
composition. In such compositions the pesticide is dissolved or
dispersed in a carrier, which is a pressure-generating propellant
mixture. The aerosol composition is packaged in a container from
which the mixture is dispensed through an atomizing valve.
Pesticide baits are formed when the pesticide is mixed with food or
an attractant or both. When the pests eat the bait they also
consume the pesticide. Baits may take the form of granules, gels,
flowable powders, liquids, or solids. They can be used in pest
harborages.
Fumigants are pesticides that have a relatively high vapor pressure
and hence can exist as a gas in sufficient concentrations to kill
pests in soil or enclosed spaces. The toxicity of the fumigant is
proportional to its concentration and the exposure time. They are
characterized by a good capacity for diffusion and act by
penetrating the pest's respiratory system or being absorbed through
the pest's cuticle. Fumigants are applied to control stored product
pests under gas proof sheets, in gas sealed rooms or buildings or
in special chambers.
Pesticides can be microencapsulated by suspending the pesticide
particles or droplets in plastic polymers of various types. By
altering the chemistry of the polymer or by changing factors in the
processing, microcapsules can be formed of various sizes,
solubility, wall thicknesses, and degrees of penetrability. These
factors govern the speed with which the active ingredient within is
released, which in turn, affects the residual performance, speed of
action, and odor of the product.
Oil solution concentrates are made by dissolving pesticide in a
solvent that will hold the pesticide in solution. Oil solutions of
a pesticide usually provide faster knockdown and kill of pests than
other formulations due to the solvents themselves having pesticidal
action and the dissolution of the waxy covering of the integument
increasing the speed of uptake of the pesticide. Other advantages
of oil solutions include better storage stability, better
penetration of crevices, and better adhesion to greasy
surfaces.
Another embodiment is an oil-in-water emulsion, wherein the
emulsion comprises oily globules which are each provided with a
lamellar liquid crystal coating and are dispersed in an aqueous
phase, wherein each oily globule comprises at least one compound
which is agriculturally active, and is individually coated with a
monolamellar or oligolamellar layer comprising: (1) at least one
non-ionic lipophilic surface-active agent, (2) at least one
non-ionic hydrophilic surface-active agent and (3) at least one
ionic surface-active agent, wherein the globules having a mean
particle diameter of less than 800 nanometers. Further information
on the embodiment is disclosed in U.S. patent publication
20070027034 published Feb. 1, 2007, having patent application Ser.
No. 11/495,228. For ease of use, this embodiment will be referred
to as "OIWE."
For further information consult "Insect Pest Management" 2nd
Edition by D. Dent, copyright CAB International (2000).
Additionally, for more detailed information consult "Handbook of
Pest Control--The Behavior, Life History, and Control of Household
Pests" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media
Inc.
Other Formulation Components
Generally, when the 1-(3-pyridyl-N-oxide)pyrazole compound of
formula I, II, or III are used in a formulation, such formulation
can also contain other components. These components include, but
are not limited to, (this is a non-exhaustive and non-mutually
exclusive list) wetters, spreaders, stickers, penetrants, buffers,
sequestering agents, drift reduction agents, compatibility agents,
anti-foam agents, cleaning agents, and emulsifiers. A few
components are described forthwith.
A wetting agent is a substance that when added to a liquid
increases the spreading or penetration power of the liquid by
reducing the interfacial tension between the liquid and the surface
on which it is spreading. Wetting agents are used for two main
functions in agrochemical formulations: during processing and
manufacture to increase the rate of wetting of powders in water to
make concentrates for soluble liquids or suspension concentrates;
and during mixing of a product with water in a spray tank to reduce
the wetting time of wettable powders and to improve the penetration
of water into water-dispersible granules. Examples of wetting
agents used in wettable powder, suspension concentrate, and
water-dispersible granule formulations are: sodium lauryl sulfate;
sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and
aliphatic alcohol ethoxylates.
A dispersing agent is a substance which adsorbs onto the surface of
particles and helps to preserve the state of dispersion of the
particles and prevents them from reaggregating. Dispersing agents
are added to agrochemical formulations to facilitate dispersion and
suspension during manufacture, and to ensure the particles
redisperse into water in a spray tank. They are widely used in
wettable powders, suspension concentrates and water-dispersible
granules. Surfactants that are used as dispersing agents have the
ability to adsorb strongly onto a particle surface and provide a
charged or steric barrier to reaggregation of particles. The most
commonly used surfactants are anionic, non-ionic, or mixtures of
the two types. For wettable powder formulations, the most common
dispersing agents are sodium lignosulfonates. For suspension
concentrates, very good adsorption and stabilization are obtained
using polyelectrolytes, such as sodium naphthalene sulfonate
formaldehyde condensates. Tristyrylphenol ethoxylate phosphate
esters are also used. Non-ionics such as alkylarylethylene oxide
condensates and EO-PO block copolymers are sometimes combined with
anionics as dispersing agents for suspension concentrates. In
recent years, new types of very high molecular weight polymeric
surfactants have been developed as dispersing agents. These have
very long hydrophobic "backbones" and a large number of ethylene
oxide chains forming the "teeth" of a "comb" surfactant. These high
molecular weight polymers can give very good long-term stability to
suspension concentrates because the hydrophobic backbones have many
anchoring points onto the particle surfaces. Examples of dispersing
agents used in agrochemical formulations are: sodium
lignosulfonates; sodium naphthalene sulfonate formaldehyde
condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic
alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and
graft copolymers.
An emulsifying agent is a substance which stabilizes a suspension
of droplets of one liquid phase in another liquid phase. Without
the emulsifying agent the two liquids would separate into two
immiscible liquid phases. The most commonly used emulsifier blends
contain alkylphenol or aliphatic alcohol with twelve or more
ethylene oxide units and the oil-soluble calcium salt of
dodecylbenzenesulfonic acid. A range of hydrophile-lipophile
balance ("HLB") values from 8 to 18 will normally provide good
stable emulsions. Emulsion stability can sometimes be improved by
the addition of a small amount of an EO-PO block copolymer
surfactant.
A solubilizing agent is a surfactant which will form micelles in
water at concentrations above the critical micelle concentration.
The micelles are then able to dissolve or solubilize
water-insoluble materials inside the hydrophobic part of the
micelle. The types of surfactants usually used for solubilization
are non-ionics, sorbitan monooleates, sorbitan monooleate
ethoxylates, and methyl oleate esters.
Surfactants are sometimes used, either alone or with other
additives such as mineral or vegetable oils as adjuvants to
spray-tank mixes to improve the biological performance of the
pesticide on the target. The types of surfactants used for
bioenhancement depend generally on the nature and mode of action of
the pesticide. However, they are often non-ionics such as: alkyl
ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine
ethoxylates.
A carrier or diluent in an agricultural formulation is a material
added to the pesticide to give a product of the required strength.
Carriers are usually materials with high absorptive capacities,
while diluents are usually materials with low absorptive
capacities. Carriers and diluents are used in the formulation of
dusts, wettable powders, granules and water-dispersible
granules.
Organic solvents are used mainly in the formulation of emulsifiable
concentrates, oil-in-water emulsions, suspoemulsions, and ultra low
volume formulations, and to a lesser extent, granular formulations.
Sometimes mixtures of solvents are used. The first main groups of
solvents are aliphatic paraffinic oils such as kerosene or refined
paraffins. The second main group (and the most common) comprises
the aromatic solvents such as xylene and higher molecular weight
fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons
are useful as cosolvents to prevent crystallization of pesticides
when the formulation is emulsified into water. Alcohols are
sometimes used as cosolvents to increase solvent power. Other
solvents may include vegetable oils, seed oils, and esters of
vegetable and seed oils.
Thickeners or gelling agents are used mainly in the formulation of
suspension concentrates, emulsions and suspoemulsions to modify the
rheology or flow properties of the liquid and to prevent separation
and settling of the dispersed particles or droplets. Thickening,
gelling, and anti-settling agents generally fall into two
categories, namely water-insoluble particulates and water-soluble
polymers. It is possible to produce suspension concentrate
formulations using clays and silicas. Examples of these types of
materials, include, but are not limited to, montmorillonite,
bentonite, magnesium aluminum silicate, and attapulgite.
Water-soluble polysaccharides have been used as thickening-gelling
agents for many years. The types of polysaccharides most commonly
used are natural extracts of seeds and seaweeds or are synthetic
derivatives of cellulose. Examples of these types of materials
include, but are not limited to, guar gum; locust bean gum;
carrageenam; alginates; methyl cellulose; sodium carboxymethyl
cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of
anti-settling agents are based on modified starches, polyacrylates,
polyvinyl alcohol and polyethylene oxide. Another good
anti-settling agent is xanthan gum.
Microorganisms can cause spoilage of formulated products. Therefore
preservation agents are used to eliminate or reduce their effect.
Examples of such agents include, but are not limited to: propionic
acid and its sodium salt; sorbic acid and its sodium or potassium
salts; benzoic acid and its sodium salt; p-hydroxybenzoic acid
sodium salt; methyl p-hydroxybenzoate; and
1,2-benzisothiazolin-3-one (BIT).
The presence of surfactants often causes water-based formulations
to foam during mixing operations in production and in application
through a spray tank. In order to reduce the tendency to foam,
anti-foam agents are often added either during the production stage
or before filling into bottles. Generally, there are two types of
anti-foam agents, namely silicones and non-silicones. Silicones are
usually aqueous emulsions of dimethyl polysiloxane, while the
non-silicone anti-foam agents are water-insoluble oils, such as
octanol and nonanol, or silica. In both cases, the function of the
anti-foam agent is to displace the surfactant from the air-water
interface.
"Green" agents (e.g., adjuvants, surfactants, solvents) can reduce
the overall environmental footprint of crop protection
formulations. Green agents are biodegradable and generally derived
from natural and/or sustainable sources, e.g. plant and animal
sources. Specific examples are: vegetable oils, seed oils, and
esters thereof, also alkoxylated alkyl polyglucosides.
For further information, see "Chemistry and Technology of
Agrochemical Formulations" edited by D. A. Knowles, copyright 1998
by Kluwer Academic Publishers. Also see "Insecticides in
Agriculture and Environment--Retrospects and Prospects" by A. S.
Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by
Springer-Verlag.
Pesticidal Activities
The disclosed pesticidal compositions may be used, for example, as
nematicides, acaricides, pesticides, insecticides, miticides,
and/or molluscicides.
In one particular embodiment, a method of controlling pests
comprises applying a pesticidal composition comprising a
1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
near a population of pests.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
are generally used in amounts from about 0.01 grams per hectare to
about 5000 grams per hectare to provide control. Amounts from about
0.1 grams per hectare to about 500 grams per hectare are generally
preferred, and amounts from about 1 gram per hectare to about 50
grams per hectare are generally more preferred.
The area to which a 1-(3-pyridyl-N-oxide)pyrazole compound of
formula I, II, or III is applied can be any area inhabited (or
maybe inhabited, or traversed by) a pest, for example: where crops,
trees, fruits, cereals, fodder species, vines, turf and ornamental
plants, are growing; where domesticated animals are residing; the
interior or exterior surfaces of buildings (such as places where
grains are stored), the materials of construction used in building
(such as impregnated wood), and the soil around buildings.
Particular crop areas to use a molecule of Formula One include
areas where apples, corn, sunflowers, cotton, soybeans, canola,
wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa,
lettuce, strawberries, tomatoes, peppers, crucifers, pears,
tobacco, almonds, sugar beets, beans and other valuable crops are
growing or the seeds thereof are going to be planted. It is also
advantageous to use ammonium sulfate with a
3-(thiazol-2-yl)pyridine 1-oxide compound when growing various
plants.
Controlling pests generally means that pest populations, pest
activity, or both, are reduced in an area. This can come about
when: pest populations are repulsed from an area; when pests are
incapacitated in or around an area; or pests are exterminated, in
whole, or in part, in or around an area. Of course, a combination
of these results can occur. Generally, pest populations, activity,
or both are desirably reduced more than fifty percent, preferably
more than 90 percent. Generally, the area is not in or on a human;
consequently, the locus is generally a non-human area.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may be used in mixtures, applied simultaneously or sequentially,
alone or with other compounds to enhance plant vigor (e.g. to grow
a better root system, to better withstand stressful growing
conditions). Such other compounds are, for example, compounds that
modulate plant ethylene receptors, most notably
1-methylcyclopropene (also known as 1-MCP). Furthermore, such
molecules may be used during times when pest activity is low, such
as before the plants that are growing begin to produce valuable
agricultural commodities. Such times include the early planting
season when pest pressure is usually low.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
can be applied to the foliar and fruiting portions of plants to
control pests. The molecules will either come in direct contact
with the pest, or the pest will consume the pesticide when eating
leaf, fruit mass, or extracting sap, that contains the pesticide.
The 3-(thiazol-2-yl)pyridine 1-oxide compound can also be applied
to the soil, and when applied in this manner, root and stem feeding
pests can be controlled. The roots can absorb a molecule taking it
up into the foliar portions of the plant to control above ground
chewing and sap feeding pests.
Generally, with baits, the baits are placed in the ground where,
for example, termites can come into contact with, and/or be
attracted to, the bait. Baits can also be applied to a surface of a
building, (horizontal, vertical, or slant surface) where, for
example, ants, termites, cockroaches, and flies, can come into
contact with, and/or be attracted to, the bait. Baits can comprise
a 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or
III.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
can be encapsulated inside, or placed on the surface of a capsule.
The size of the capsules can range from nanometer size (about
100-900 nanometers in diameter) to micrometer size (about 10-900
microns in diameter).
Because of the unique ability of the eggs of some pests to resist
certain pesticides, repeated applications of the
1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III may
be desirable to control newly emerged larvae.
Systemic movement of pesticides in plants may be utilized to
control pests on one portion of the plant by applying (for example
by spraying an area) the 1-(3-pyridyl-N-oxide)pyrazole compound of
formula I, II, or III to a different portion of the plant. For
example, control of foliar-feeding insects can be achieved by drip
irrigation or furrow application, by treating the soil with for
example pre- or post-planting soil drench, or by treating the seeds
of a plant before planting.
Seed treatment can be applied to all types of seeds, including
those from which plants genetically modified to express specialized
traits will germinate. Representative examples include those
expressing proteins toxic to invertebrate pests, such as Bacillus
thuringiensis or other insecticidal toxins, those expressing
herbicide resistance, such as "Roundup Ready" seed, or those with
"stacked" foreign genes expressing insecticidal toxins, herbicide
resistance, nutrition-enhancement, drought resistance, or any other
beneficial traits. Furthermore, such seed treatments with the
1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III may
further enhance the ability of a plant to better withstand
stressful growing conditions. This results in a healthier, more
vigorous plant, which can lead to higher yields at harvest time.
Generally, about 1 gram of the 1-(3-pyridyl-N-oxide)pyrazole
compound of formula I, II, or III to about 500 grams per 100,000
seeds is expected to provide good benefits, amounts from about 10
grams to about 100 grams per 100,000 seeds is expected to provide
better benefits, and amounts from about 25 grams to about 75 grams
per 100,000 seeds is expected to provide even better benefits.
It should be readily apparent that the
1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III may
be used on, in, or around plants genetically modified to express
specialized traits, such as Bacillus thuringiensis or other
insecticidal toxins, or those expressing herbicide resistance, or
those with "stacked" foreign genes expressing insecticidal toxins,
herbicide resistance, nutrition-enhancement, or any other
beneficial traits.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may be used for controlling endoparasites and ectoparasites in the
veterinary medicine sector or in the field of non-human animal
keeping. The 3-(thiazol-2-yl)pyridine 1-oxide compound are applied,
such as by oral administration in the form of, for example,
tablets, capsules, drinks, granules, by dermal application in the
form of, for example, dipping, spraying, pouring on, spotting on,
and dusting, and by parenteral administration in the form of, for
example, an injection.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may also be employed advantageously in livestock keeping, for
example, cattle, sheep, pigs, chickens, and geese. They may also be
employed advantageously in pets such as, horses, dogs, and cats.
Particular pests to control would be fleas and ticks that are
bothersome to such animals. Suitable formulations are administered
orally to the animals with the drinking water or feed. The dosages
and formulations that are suitable depend on the species.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may also be used for controlling parasitic worms, especially of the
intestine, in the animals listed above.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may also be employed in therapeutic methods for human health care.
Such methods include, but are limited to, oral administration in
the form of, for example, tablets, capsules, drinks, granules, and
by dermal application.
Pests around the world have been migrating to new environments (for
such pest) and thereafter becoming a new invasive species in such
new environment. The 1-(3-pyridyl-N-oxide)pyrazole compound of
formula I, II, or III may also be used on such new invasive species
to control them in such new environment.
The 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
may also be used in an area where plants, such as crops, are
growing (e.g. pre-planting, planting, pre-harvesting) and where
there are low levels (even no actual presence) of pests that can
commercially damage such plants. The use of such molecules in such
area is to benefit the plants being grown in the area. Such
benefits, may include, but are not limited to, improving the health
of a plant, improving the yield of a plant (e.g. increased biomass
and/or increased content of valuable ingredients), improving the
vigor of a plant (e.g. improved plant growth and/or greener
leaves), improving the quality of a plant (e.g. improved content or
composition of certain ingredients), and improving the tolerance to
abiotic and/or biotic stress of the plant.
Before a pesticide can be used or sold commercially, such pesticide
undergoes lengthy evaluation processes by various governmental
authorities (local, regional, state, national, and international).
Voluminous data requirements are specified by regulatory
authorities and must be addressed through data generation and
submission by the product registrant or by a third party on the
product registrant's behalf, often using a computer with a
connection to the World Wide Web. These governmental authorities
then review such data and if a determination of safety is
concluded, provide the potential user or seller with product
registration approval. Thereafter, in that locality where the
product registration is granted and supported, such user or seller
may use or sell such pesticide.
A 1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III
can be tested to determine its efficacy against pests. Furthermore,
mode of action studies can be conducted to determine if said
molecule has a different mode of action than other pesticides.
Thereafter, such acquired data can be disseminated, such as by the
internet, to third parties.
The disclosed pesticidal composition comprising a
1-(3-pyridyl-N-oxide)pyrazole compound of formula I, II, or III may
be used to control a wide variety of pests.
As a non-limiting example, in one or more embodiments, the method
of the present disclosure may be used to control one or more
members of Lyriomiza sativae, Caliothrips phaseoli, Paratrioza
cockerel, Spodoptera exigua, Myzus persicae, Nilaparvata lugens,
and Bermisia tabaci.
In additional embodiments, the method of the present disclosure may
be used to control one or more members of at least one of Phylum
Arthropoda, Phylum Nematoda, Subphylum Chelicerata, Subphylum
Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida, and
Class Symphyla. In at least some embodiments, the method of the
present disclosure may be used to control one or more members of at
least one of Class Insecta and Class Arachnida.
In further embodiments, the method of the present disclosure may be
used to control members of the Order Coleoptera (beetles)
including, but not limited to, Acanthoscelides spp. (weevils),
Acanthoscelides obtectus (common bean weevil), Agrilus planipennis
(emerald ash borer), Agriotes spp. (wireworms), Anoplophora
glabripennis (Asian longhorned beetle), Anthonomus spp. (weevils),
Anthonomus grandis (boll weevil), Aphidius spp., Apion spp.
(weevils), Apogonia spp. (grubs), Ataenius spretulus (Black
Turfgrass Ataenius), Atomaria linearis (pygmy mangold beetle),
Aulacophore spp., Bothynoderes punctiventris (beet root weevil),
Bruchus spp. (weevils), Bruchus pisorum (pea weevil), Cacoesia
spp., Callosobruchus maculates (southern cow pea weevil),
Carpophilus hemipteras (dried fruit beetle), Cassida vittata,
Cerosterna spp., Cerotoma spp. (chrysomelids), Cerotoma trifurcata
(bean leaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus
assimilis (cabbage seedpod weevil), Ceutorhynchus napi (cabbage
curculio), Chaetocnema spp. (chrysomelids), Colaspis spp. (soil
beetles), Conoderus scalaris, Conoderus stigmosus, Conotrachelus
nenuphar (plum curculio), Cotinus nitidis (Green June beetle),
Crioceris asparagi (asparagus beetle), Cryptolestes ferrugineus
(rusty grain beetle), Cryptolestes pusillus (flat grain beetle),
Cryptolestes turcicus (Turkish grain beetle), Ctenicera spp.
(wireworms), Curculio spp. (weevils), Cyclocephala spp. (grubs),
Cylindrocpturus adspersus (sunflower stem weevil), Deporaus
marginatus (mango leaf-cutting weevil), Dermestes lardarius (larder
beetle), Dermestes maculates (hide beetle), Diabrotica spp.
(chrysomelids), Epilachna varivestis (Mexican bean beetle),
Faustinus cubae, Hylobius pales (pales weevil), Hypera spp.
(weevils), Hypera postica (alfalfa weevil), Hyperdoes spp.
(Hyperodes weevil), Hypothenemus hampei (coffee berry beetle), Ips
spp. (engravers), Lasioderma serricorne (cigarette beetle),
Leptinotarsa decemlineata (Colorado potato beetle), Liogenys
fuscus, Liogenys suturalis, Lissorhoptrus oryzophilus (rice water
weevil), Lyctus spp. (wood beetles/powder post beetles),
Maecolaspis joliveti, Megascelis spp., Melanotus communis,
Meligethes spp., Meligethes aeneus (blossom beetle), Melolontha
melolontha (common European cockchafer), Oberea brevis, Oberea
linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilus
mercator (merchant grain beetle), Oryzaephilus surinamensis
(sawtoothed grain beetle), Otiorhynchus spp. (weevils), Oulema
melanopus (cereal leaf beetle), Oulema oryzae, Pantomorus spp.
(weevils), Phyllophaga spp. (May/June beetle), Phyllophaga cuyabana
(chrysomelids), Phynchites spp., Popillia japonica (Japanese
beetle), Prostephanus truncates (larger grain borer), Rhizopertha
dominica (lesser grain borer), Rhizotrogus spp. (European chafer),
Rhynchophorus spp. (weevils), Scolytus spp. (wood beetles),
Shenophorus spp. (Billbug), Sitona lineatus (pea leaf weevil),
Sitophilus spp. (grain weevils), Sitophilus granaries (granary
weevil), Sitophilus oryzae (rice weevil), Stegobium paniceum
(drugstore beetle), Tribolium spp. (flour beetles), Tribolium
castaneum (red flour beetle), Tribolium confusum (confused flour
beetle), Trogoderma variabile (warehouse beetle), and Zabrus
tenebioides.
In other embodiments, the method of the present disclosure may also
be used to control members of the Order Dermaptera (earwigs).
In additional embodiments, the method of the present disclosure may
be used to control members of the Order Dictyoptera (cockroaches)
including, but is not limited to, Blattella germanica (German
cockroach), Blatta orientalis (oriental cockroach), Parcoblatta
pennylvanica, Periplaneta americana (American cockroach),
Periplaneta australoasiae (Australian cockroach), Periplaneta
brunnea (brown cockroach), Periplaneta fuliginosa (smokybrown
cockroach), Pyncoselus suninamensis (Surinam cockroach), and
Supella longipalpa (brownbanded cockroach).
In further embodiments, the method of the present disclosure may be
used to control members of the Order Diptera (true flies)
including, but is not limited to, Aedes spp. (mosquitoes), Agromyza
frontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner
flies), Anastrepha spp. (fruit flies), Anastrepha suspensa
(Caribbean fruit fly), Anopheles spp. (mosquitoes), Batrocera spp.
(fruit flies), Bactrocera cucurbitae (melon fly), Bactrocera
dorsalis (oriental fruit fly), Ceratitis spp. (fruit flies),
Ceratitis capitata (Mediterranean fruit fly), Chrysops spp. (deer
flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gall
midges), Culex spp. (mosquitoes), Dasineura spp. (gall midges),
Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura
(seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp.
(filth flies), Fannia canicularis (little house fly), Fannia
scalaris (latrine fly), Gasterophilus intestinalis (horse bot fly),
Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp.
(root maggots), Hypoderma lineatum (common cattle grub), Liriomyza
spp. (leafminer flies), Liriomyza brassica (serpentine leafminer),
Melophagus ovinus (sheep ked), Musca spp. (muscid flies), Musca
autumnalis (face fly), Musca domestica (house fly), Oestrus ovis
(sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beet
leafminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletis
cerasi (cherry fruit fly), Rhagoletis pomonella (apple maggot),
Sitodiplosis mosellana (orange wheat blossom midge), Stomoxys
calcitrans (stable fly), Tabanus spp. (horse flies), and Tipula
spp. (crane flies).
In other embodiments, the method of the present disclosure may be
used to control members of the Order Hemiptera (true bugs)
including, but is not limited to, Acrosternum hilare (green stink
bug), Blissus leucopterus (chinch bug), Calocoris norvegicus
(potato mirid), Cimex hemipterus (tropical bed bug), Cimex
lectularius (bed bug), Dagbertus fasciatus, Dichelops furcatus,
Dysdercus suturellus (cotton stainer), Edessa meditabunda,
Eurygaster maura (cereal bug), Euschistus heros, Euschistus servus
(brown stink bug), Helopeltis antonii, Helopeltis theivora (tea
blight plantbug), Lagynotomus spp. (stink bugs), Leptocorisa
oratorius, Leptocorisa varicornis, Lygus spp. (plant bugs), Lygus
hesperus (western tarnished plant bug), Maconellicoccus hirsutus,
Neurocolpus longirostris, Nezara viridula (southern green stink
bug), Phytocoris spp. (plant bugs), Phytocoris californicus,
Phytocoris relativus, Piezodorus guildingi, Poecilocapsus lineatus
(fourlined plant bug), Psallus vaccinicola, Pseudacysta perseae,
Scaptocoris castanea, and Triatoma spp. (bloodsucking conenose
bugs/kissing bugs).
In additional embodiments, the method of the present disclosure may
be used to control members of the Order Homoptera (aphids, scales,
whiteflies, leaflhoppers) including, but is not limited to,
Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodes
proletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixus
floccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutella
bigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii
(California red scale), Aphis spp. (aphids), Aphis gossypii (cotton
aphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove
aphid), Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia
tabaci (sweetpotato whitefly), Brachycolus noxius (Russian aphid),
Brachycorynella asparagi (asparagus aphid), Brevennia rehi,
Brevicoryne brassicae (cabbage aphid), Ceroplastes spp. (scales),
Ceroplastes rubens (red wax scale), Chionaspis spp. (scales),
Chrysomphalus spp. (scales), Coccus spp. (scales), Dysaphis
plantaginea (rosy apple aphid), Empoasca spp. (leafhoppers),
Eriosoma lanigerum (woolly apple aphid), Icerya purchasi (cottony
cushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphax
striatellus (smaller brown planthopper), Lepidosaphes spp.,
Macrosiphum spp., Macrosiphum euphorbiae (potato aphid),
Macrosiphum granarium (English grain aphid), Macrosiphum rosae
(rose aphid), Macrosteles quadrilineatus (aster leafhopper),
Mahanarva frimbiolata, Metopolophium dirhodum (rose grain aphid),
Mictis longicornis, Myzus spp., Myzus persicae (green peach aphid),
Nephotettix spp. (leafhoppers), Nephotettix cinctipes (green
leafhopper), Nilaparvata lugens (brown planthopper), Parlatoria
pergandii (chaff scale), Parlatoria ziziphi (ebony scale),
Peregrinus maidis (corn delphacid), Philaenus spp. (spittlebugs),
Phylloxera vitifoliae (grape phylloxera), Physokermes piceae
(spruce bud scale), Planococcus spp. (mealybugs), Pseudococcus spp.
(mealybugs), Pseudococcus brevipes (pine apple mealybug),
Quadraspidiotus perniciosus (San Jose scale), Rhapalosiphum spp.
(aphids), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi
(oat bird-cherry aphid), Saissetia spp. (scales), Saissetia oleae
(black scale), Schizaphis graminum (greenbug), Sitobion avenae
(English grain aphid), Sogatella furcifera (white-backed
planthopper), Therioaphis spp. (aphids), Toumeyella spp. (scales),
Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies),
Trialeurodes vaporariorum (greenhouse whitefly), Trialeurodes
abutiloneus (bandedwing whitefly), Unaspis spp. (scales), Unaspis
yanonensis (arrowhead scale), and Zulia entreriana. In at least
some embodiments, the method of the present disclosure may be used
to control Myzus persicae.
In other embodiments, the method of the present disclosure may be
used to control members of the Order Hymenoptera (ants, wasps, and
bees) including, but not limited to, Acromyrrmex spp., Athalia
rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpenter
ants), Diprion spp. (sawflies), Formica spp. (ants), Iridomyrmex
humilis (Argentine ant), Monomorium ssp., Monomorium minumum
(little black ant), Monomorium pharaonic (Pharaoh ant), Neodiprion
spp. (sawflies), Pogonomyrmex spp. (harvester ants), Polistes spp.
(paper wasps), Solenopsis spp. (fire ants), Tapoinoma sessile
(odorous house ant), Tetranomorium spp. (pavement ants), Vespula
spp. (yellow jackets), and Xylocopa spp. (carpenter bees).
In certain embodiments, the method of the present disclosure may be
used to control members of the Order Isoptera (termites) including,
but not limited to, Coptotermes spp., Coptotermes curvignathus,
Coptotermes frenchii, Coptotermes formosanus (Formosan subterranean
termite), Cornitermes spp. (nasute termites), Cryptotermes spp.
(drywood termites), Heterotermes spp. (desert subterranean
termites), Heterotermes aureus, Kalotermes spp. (drywood termites),
Incistitermes spp. (drywood termites), Macrotermes spp. (fungus
growing termites), Marginitermes spp. (drywood termites),
Microcerotermes spp. (harvester termites), Microtermes obesi,
Procornitermes spp., Reticulitermes spp. (subterranean termites),
Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes
flavipes (eastern subterranean termite), Reticulitermes hageni,
Reticulitermes hesperus (western subterranean termite),
Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes
tibialis, Reticulitermes virginicus, Schedorhinotermes spp., and
Zootermopsis spp. (rotten-wood termites).
In additional embodiments, the method of the present disclosure may
be used to control members of the Order Lepidoptera (moths and
butterflies) including, but not limited to, Achoea janata,
Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotis
ipsilon (black cutworm), Alabama argillacea (cotton leafworm),
Amorbia cuneana, Amyelosis transitella (navel orangeworm),
Anacamptodes defectaria, Anarsia lineatella (peach twig borer),
Anomis sabulifera (jute looper), Anticarsia gemmatalis (velvetbean
caterpillar), Archips argyrospila (fruittree leafroller), Archips
rosana (rose leaf roller), Argyrotaenia spp. (tortricid moths),
Argyrotaenia citrana (orange tortrix), Autographa gamma, Bonagota
cranaodes, Borbo cinnara (rice leaf folder), Bucculatrix
thurberiella (cotton leafperforator), Caloptilia spp. (leaf
miners), Capua reticulana, Carposina niponensis (peach fruit moth),
Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneura
rosaceana (obliquebanded leafroller), Chrysodeixis spp.,
Cnaphalocerus medinalis (grass leafroller), Colias spp.,
Conpomorpha cramerella, Cossus cossus (carpenter moth), Crambus
spp. (Sod webworms), Cydiafunebrana (plum fruit moth), Cydia
molesta (oriental fruit moth), Cydia nignicana (pea moth), Cydia
pomonella (codling moth), Darna diducta, Diaphania spp. (stem
borers), Diatraea spp. (stalk borers), Diatraea saccharalis
(sugarcane borer), Diatraea graniosella (southwester corn borer),
Earias spp. (bollworms), Earias insulata (Egyptian bollworm),
Earias vitella (rough northern bollworm), Ecdytopopha aurantianum,
Elasmopalpus lignosellus (lesser cornstalk borer), Epiphysias
postruttana (light brown apple moth), Ephestia spp. (flour moths),
Ephestia cautella (almond moth), Ephestia elutella (tobbaco moth),
Ephestia kuehniella (Mediterranean flour moth), Epimeces spp.,
Epinotia aporema, Erionota thrax (banana skipper), Eupoecilia
ambiguella (grape berry moth), Euxoa auxiliaris (army cutworm),
Feltia spp. (cutworms), Gortyna spp. (stemborers), Grapholita
molesta (oriental fruit moth), Hedylepta indicata (bean leaf
webber), Helicoverpa spp. (noctuid moths), Helicoverpa armigera
(cotton bollworm), Helicoverpa zea (bollworm/corn earworm),
Heliothis spp. (noctuid moths), Heliothis virescens (tobacco
budworm), Hellula undalis (cabbage webworm), Indarbela spp. (root
borers), Keiferia lycopersicella (tomato pinworm), Leucinodes
orbonalis (eggplant fruit borer), Leucoptera malifoliella,
Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis
spp. (noctuid moths), Loxagrotis albicosta (western bean cutworm),
Lymantria dispar (gypsy moth), Lyonetia clerkella (apple leaf
miner), Mahasena corbetti (oil palm bagworm), Malacosoma spp. (tent
caterpillars), Mamestra brassicae (cabbage armyworm), Maruca
testulalis (bean pod borer), Metisa plana (bagworm), Mythimna
unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato
borer), Nymphula depunctalis (rice caseworm), Operophthera brumata
(winter moth), Ostrinia nubilalis (European corn borer), Oxydia
vesulia, Pandemis cerasana (common currant tortrix), Pandemis
heparana (brown apple tortrix), Papilio demodocus, Pectinophora
gossypiella (pink bollworm), Peridroma spp. (cutworms), Peridroma
saucia (variegated cutworm), Perileucoptera coffeella (white coffee
leafminer), Phthorimaea operculella (potato tuber moth),
Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris
rapae (imported cabbageworm), Plathypena scabra, Plodia
interpunctella (Indian meal moth), Plutella xylostella (diamondback
moth), Polychrosis viteana (grape berry moth), Prays endocarpa,
Prays oleae (olive moth), Pseudaletia spp. (noctuid moths),
Pseudaletia unipunctata (armyworm), Pseudoplusia includens (soybean
looper), Rachiplusia nu, Scirpophaga incertulas, Sesamia spp.
(stemborers), Sesamia inferens (pink rice stem borer), Sesamia
nonagrioides, Setora nitens, Sitotroga cerealella (Angoumois grain
moth), Sparganothis pilleriana, Spodoptera spp. (armyworms),
Spodoptera exigua (beet armyworm), Spodoptera fugiperda (fall
armyworm), Spodoptera oridania (southern armyworm), Synanthedon
spp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineola
bisselliella (webbing clothes moth), Trichoplusia ni (cabbage
looper), Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red
branch borer), and Zeuzera pyrina (leopard moth). In at least some
embodiments, the method of the present disclosure may be used to
control Spodoptera exigua.
The method of the present disclosure may be used to also control
members of the Order Mallophaga (chewing lice) including, but not
limited to, Bovicola ovis (sheep biting louse), Menacanthus
stramineus (chicken body louse), and Menopon gallinea (common hen
louse).
In additional embodiments, the method of the present disclosure may
be used to control members of the Order Orthoptera (grasshoppers,
locusts, and crickets) including, but not limited to, Anabrus
simplex (Mormon cricket), Gryllotalpidae (mole crickets), Locusta
migratoria, Melanoplus spp. (grasshoppers), Microcentrum retinerve
(angularwinged katydid), Pterophylla spp. (kaydids), chistocerca
gregaria, Scudderia furcata (forktailed bush katydid), and Valanga
nigricorni.
In other embodiments, the method of the present disclosure may be
used to control members of the Order Phthiraptera (sucking lice)
including, but not limited to, Haematopinus spp. (cattle and hog
lice), Linognathus ovillus (sheep louse), Pediculus humanus capitis
(human body louse), Pediculus humanus humanus (human body lice),
and Pthirus pubis (crab louse).
In particular embodiments, the method of the present disclosure may
be used to control members of the Order Siphonaptera (fleas)
including, but not limited to, Ctenocephalides canis (dog flea),
Ctenocephalides felis (cat flea), and Pulex irritans (human
flea).
In additional embodiments, the method of the present disclosure may
be used to control members of the Order Thysanoptera (thrips)
including, but not limited to, Frankliniella fusca (tobacco
thrips), Frankliniella occidentalis (western flower thrips),
Frankliniella shultzei, Frankliniella williamsi (corn thrips),
Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothrips
cruentatus, Scirtothrips spp., Scirtothrips citri (citrus thrips),
Scirtothrips dorsalis (yellow tea thrips), Taeniothrips
rhopalantennalis, and Thrips spp.
The method of the present disclosure may be used to also control
members of the Order Thysanura (bristletails) including, but not
limited to, Lepisma spp. (silverfish) and Thermobia spp.
(firebrats).
In further embodiments, the method of the present disclosure may be
used to control members of the Order Acari (mites and ticks)
including, but not limited to, Acarapsis woodi (tracheal mite of
honeybees), Acarus spp. (food mites), Acarus siro (grain mite),
Aceria mangiferae (mango bud mite), Aculops spp., Aculops
lycopersici (tomato russet mite), Aculops pelekasi, Aculus
pelekassi, Aculus schlechtendali (apple rust mite), Amblyomma
americanum (lone star tick), Boophilus spp. (ticks), Brevipalpus
obovatus (privet mite), Brevipalpus phoenicis (red and black flat
mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks),
Dermacentor variabilis (american dog tick), Dermatophagoides
pteronyssinus (house dust mite), Eotetranycus spp., Eotetranychus
carpini (yellow spider mite), Epitimerus spp., Eriophyes spp.,
Ixodes spp. (ticks), Metatetranycus spp., Notoedres cati,
Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (southern
red mite), Panonychus spp., Panonychus citri (citrus red mite),
Panonychus ulmi (European red mite), Phyllocoptruta oleivora
(citrus rust mite), Polyphagotarsonemun latus (broad mite),
Rhipicephalus sanguineus (brown dog tick), Rhizoglyphus spp. (bulb
mites), Sarcoptes scabiei (itch mite), Tegolophus perseaflorae,
Tetranychus spp., Tetranychus urticae (twospotted spider mite), and
Varroa destructor (honey bee mite).
In additional embodiments, the method of the present disclosure may
be used to control members of the Order Nematoda (nematodes)
including, but not limited to, Aphelenchoides spp. (foliar
nematodes), Belonolaimus spp. (sting nematodes), Criconemella spp.
(ring nematodes), Dirofilaria immitis (dog heartworm),
Ditylenchusspp. (stem and bulb nematodes), Heterodera spp. (cyst
nematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella
spp. (root nematodes), Hoplolaimus spp. (lance nematodes),
Meloidogyne spp. (root knot nematodes), Meloidogyne incognita (root
knot nematode), Onchocerca volvulus (hook-tail worm), Pratylenchus
spp. (lesion nematodes), Radopholus spp. (burrowing nematodes), and
Rotylenchus reniformis (kidney-shaped nematode).
In at least some embodiments, the method of the present disclosure
may be used to control at least one insect in one or more of the
Orders Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera,
Isoptera, Orthoptera, Diptera, Hymenoptera, and Siphonaptera, and
at least one mite in the Order Acari.
DETAILED DESCRIPTION
Insecticidal Testing
Example A
Bioassay for Green Peach Aphid (Myzus persicae) (GPA) (MYZUPE)
The green peach aphid (Myzus persicae) is the most significant
aphid pest of peach trees, causing decreased growth, shriveling of
the leaves, and the death of various tissues. It is also hazardous
because it acts as a vector for the transport of plant viruses,
such as potato virus Y and potato leafroll virus to members of the
nightshade/potato family Solanaceae, and various mosaic viruses to
many other food crops. GPA attacks such plants as broccoli,
burdock, cabbage, carrot, cauliflower, daikon, eggplant, green
beans, lettuce, macadamia, papaya, peppers, sweet potatoes,
tomatoes, watercress, and zucchini, among other plants. GPA also
attacks many ornamental crops such as carnation, chrysanthemum,
flowering white cabbage, poinsettia, and roses. GPA has developed
resistance to many pesticides.
Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm)
true leaves, were used as test substrate. The seedlings were
infested with 20-50 GPA (wingless adult and nymph stages) one day
prior to chemical application. Four pots with individual seedlings
were used for each treatment. Test compounds (2 mg) were dissolved
in 2 mL of acetone/methanol (1:1) solvent, forming stock solutions
of 1000 ppm test compound. The stock solutions were diluted
5.times. with 0.025% Tween 20 in H.sub.2O to obtain the solution at
200 ppm test compound. A hand-held aspirator-type sprayer was used
for spraying a solution to both sides of cabbage leaves until
runoff. Reference plants (solvent check) were sprayed with the
diluent only containing 20% by volume of acetone/methanol (1:1)
solvent. Treated plants were held in a holding room for three days
at approximately 25.degree. C. and ambient relative humidity (RH)
prior to grading. Evaluation was conducted by counting the number
of live aphids per plant under a microscope. Percent control was
measured by using Abbott's correction formula (W. S. Abbott, "A
Method of Computing the Effectiveness of an Insecticide," J. Econ.
Entomol. 18 (1925), pp. 265-267) as follows. Corrected %
Control=100*(X-Y)/X
where
X=No. of live aphids on solvent check plants and
Y=No. of live aphids on treated plants
The results are indicated in the table entitled "TABLE 2.
Biological Data for Green Peach Aphid (GPA) (MYZUPE) and
Sweetpotato Whitefly-crawler (WF) (BEMITA)" (See Table
Section).
Example B
Insecticidal Test for Sweetpotato Whitefly-Crawler (WF) (Bemisia
tabaci) (BEMITA) in Foliar Spray Assay
The sweetpotato whitefly (Bemisia tabaci) has been reported as a
serious pest of cultivated crops world-wide. It has an extremely
wide host range attacking more than 500 species of plants from 63
plant families. Weeds often serve as alternate hosts of crop pests.
Direct feeding damage is caused by the piercing and sucking sap
from the foliage of plants. This feeding causes weakening and early
wilting of the plant and reduces the plant growth rate and yield.
Indirect damage results by the accumulation of honeydew produced by
the whiteflies. Honeydew serves as a substrate for the growth of
black sooty mold on leaves and fruit reducing photosynthesis and
lessens the market value of the plant or yield. Damage is also
caused when sweetpotato whitefly vectors plant viruses. The
sweetpotato whitefly is considered the most common and important
whitefly vector of plant viruses worldwide.
Cotton plants (Gossypium hirsutum) grown in 3-inch pots, with 1
small (4-5 cm) true leaves, were used as test substrate. The plants
were infested with 200-400 whitefly eggs 4-5 days prior to chemical
application. Four pots with individual plants were used for each
treatment. Test compounds (2 mg) were dissolved in 1 mL of acetone
solvent, forming stock solutions of 2000 ppm test compound. The
stock solutions were diluted 10.times. with 0.025% Tween 20 in
H.sub.2O (diluents) to obtain the solution at 200 ppm test
compound. A hand-held aspirator-type sprayer was used for spraying
a solution to both sides of cotton leaves until runoff. Reference
plants (solvent check) were sprayed with the diluent only
containing 10% by volume of acetone solvent. Treated plants were
held in a holding room for 9 days at approximately 25.degree. C.
and ambient relative humidity (RH) prior to grading. Evaluation was
conducted by counting the number of live 3-4 nymph stage per plant
under a microscope. Percent control was measured by using Abbott's
correction formula (W. S. Abbott, "A Method of Computing the
Effectiveness of an Insecticide," J. Econ. Entomol. 18 (1925), pp.
265-267) as follows. Corrected % Control=100*(X-Y)/X
where
X=No. of live nymphs on solvent check plants and
Y=No. of live nymphs on treated plants.
The results are indicated in the table entitled "TABLE 2.
Biological Data for Green Peach Aphid (GPA) (MYZUPE) and
Sweetpotato Whitefly-crawler (WF) (BEMITA)" (See Table
Section).
The mortality efficiency of the disclosed pesticidal compounds
against GPA and WF insects was rated as shown in TABLE 1.
TABLE-US-00001 TABLE 1 % Control (or Mortality) Rating 80-100 A
More than 0 - Less than 80 B Not Tested C No activity noticed in
this bioassay D
TABLE-US-00002 TABLE 2 Biological Data for GPA (MYZUPE) and
WF-crawler (BEMITA) Insect Species GPA WF No. 200 ppm 200 ppm F1 A
A F2 A A F4 A A F5 A A F6 A A F7 A B F8 A A F9 A A F10 A A F11 A A
F12 A A F13 A A C1 B B P1 A A P2 A A P9 A A P10 A A P18 A A P19 A A
P36 A A P37 A A P48 A A P49 A A P50 A A P53 A A P54 A A P56 A A P57
A A P62 A A P63 A A P65 A A P66 A A P71 A A P72 A A P74 A A P75 A A
P80 A A P81 A A P92 A A P93 A A P98 B A P99 A A FA1 A A FA2 A A FA3
A A FA4 A A FA5 A A FA6 A A FA7 A A FA8 A A FA9 A A FA10 A B FA11 A
B FA12 A A FA13 A C FA14 A C CA1 B B CA2 B A CA3 A B CA4 B B
EXAMPLES
These examples are for illustration purposes and are not to be
construed as limiting the disclosure to only the embodiments
disclosed in these examples.
Starting materials, reagents, and solvents that were obtained from
commercial sources were used without further purification.
Anhydrous solvents were purchased as SURE/SEAL.TM. from Aldrich and
were used as received. Melting points were obtained on a Thomas
Hoover Unimelt capillary melting point apparatus or an OptiMelt
Automated Melting Point System from Stanford Research Systems and
are uncorrected. Examples using "room temperature" were conducted
in climate controlled laboratories with a temperature of from about
20.degree. C. to about 24.degree. C. Molecules are given their
known names, named according to naming programs within ISIS Draw,
ChemDraw or ACD Name Pro. If such programs are unable to name a
molecule, the molecule is named using conventional naming rules.
.sup.1H NMR spectral data are in ppm (.delta.) and were recorded at
300, 400 or 600 MHz. .sup.13C NMR spectral data are in ppm
(.delta.) and were recorded at 75, 100 or 150 MHz. .sup.19F NMR
spectral data are in ppm (.delta.) and were recorded at 376 MHz,
unless otherwise stated.
Example 1
Preparation of 3-(3-chloro-4-(ethylamino)-1H-pyrazol-1-yl)pyridine
1-oxide
Compound C1
##STR00010##
To a solution of
3-(4-((tert-butoxycarbonyl)(ethyl)amino)-3-chloro-1H-pyrazol-1-yl)pyridin-
e 1-oxide (prepared as described in the PCT Publication No. WO
2012/108511) (0.459 g, 1.36 mmol) in CH.sub.2Cl.sub.2 (13.5 mL) at
a temperature of about 0.degree. C. was added TFA (1.04 mL, 13.6
mmol). The reaction was allowed to warm to room temperature and
stirred for 18 hours. The reaction was diluted with toluene (10 mL)
and concentrated to dryness under reduced pressure. The residue was
taken up in CH.sub.2Cl.sub.2 (100 mL) and washed with saturated
aqueous sodium bicarbonate (NaHCO.sub.3, 100 mL). The layers were
separated, and the organic phases were dried over sodium sulfate
(Na.sub.2SO.sub.4), filtered, and concentrated under reduced
pressure to provide the title compound Cl as a tan solid (0.278 g,
85%): mp 148.degree. C.-153.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.55 (t, J=1.8 Hz, 1H), 8.04 (ddd, J=6.4, 1.7,
0.9 Hz, 1H), 7.52 (ddd, J=8.5, 2.0, 0.9 Hz, 1H), 7.33-7.27 (m, 1H),
7.19 (s, 1H), 3.17-2.97 (m, 3H), 1.30 (t, J=6.8 Hz, 3H); ESIMS m/z
239 ([M+H].sup.+).
The following molecules were made in accordance with the procedures
disclosed in Example 1, supra:
##STR00011##
3-(3-Chloro-4-(prop-2-yn-1-ylamino)-1H-pyrazol-1-yl)pyridine
1-oxide (Compound CA1) was isolated (4.0 g, 82%): mp
167-173.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.58
(d, J=2.0 Hz, 1H), 8.06 (d, J=6.4 Hz, 1H), 7.56 (dd, J=8.0, 1.6 Hz,
1H), 7.42 (s, 1H), 7.30 (dd, J=8.0, 6.4 Hz, 1H), 3.98 (d, J=2.4 Hz,
2H), 2.30 (t, J=2.4 Hz, 1H), NH not observed; ESIMS m/z 249
([M+H].sup.+).
##STR00012##
3-(4-(Ethylamino)-3-methyl-1H-pyrazol-1-yl)pyridine 1-oxide
(Compound CA2) was isolated as a light brown solid (5.40 g, 87%):
mp 105-108.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta.
8.58 (s, 1H), 7.98 (dd, J=8.4, 1.2 Hz, 1H), 7.52 (dd, J=8.4, 1.2
Hz, 1H), 7.25 (s, 1H), 7.22 (d, J=8.4 Hz, 1H), 3.06 (q, J=7.2 Hz,
2H), 2.23 (s, 3H), 1.30 (t, J=7.2 Hz, 3H), NH not observed; ESIMS
m/z 219 ([M+H].sup.+).
##STR00013##
3-(3-Chloro-4-(methylamino)-1H-pyrazol-1-yl)pyridine 1-oxide
(Compound CA3) was isolated (2.5 g, 58%): mp 142-145.degree. C.;
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.56 (d, J=1.6 Hz, 1H),
8.04 (d, J=6.4 Hz, 1H), 7.52 (dd, J=8.0, 1.6 Hz, 1H), 7.28 (dd,
J=8.0, 6.4 Hz, 1H), 7.21 (s, 1H), 2.85 (s, 3H), NH not observed;
ESIMS m/z 225 ([M+H].sup.+).
##STR00014##
3-(3-Chloro-4-(ethylamino)-1H-pyrazol-1-yl)-5-fluoropyridine
1-oxide (Compound CA4) was isolated as an off-white solid (4.0 g,
100%): mp 134-146.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.39 (s, 1H), 7.96 (dd, J=3.6, 1.6 Hz, 1H), 7.36 (dd,
J=3.6, 1.6 Hz, 1H), 7.14 (s, 1H), 3.60 (q, J=7.2 Hz, 2H), 1.38 (t,
J=7.2 Hz, 3H), NH not observed; ESIMS m/z 257 ([M+H].sup.+).
Example 2
Preparation of
S-(1-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropa-
n-2-yl)ethanethioate
Compound C3
##STR00015##
To a solution of
2-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide
(1.00 g, 3.19 mmol) in acetone (6.4 mL) was added potassium
ethanethioate (0.438 g, 3.83 mmol). The reaction vessel was capped
and heated at a temperature of about 60.degree. C. for 1.5 hours.
The reaction was cooled to room temperature and poured into a
separatory funnel containing water (20 mL) and EtOAc (20 mL). The
layers were separated, and aqueous layer was extracted with EtOAc
(3.times.20 mL). The combined organic extract was dried over
anhydrous Na.sub.2SO.sub.4, filtered, and concentrated under
reduced pressure. The crude residue was purified via flash
chromatography (SiO.sub.2) eluting with 20-100% EtOAc/hexanes to
give the title molecule C3 as brown, highly viscous oil (1.07 g,
90%).
Example 3
Preparation of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-((2,2,2-trifluoro-
ethyl)thio)propanamide
Compound C4
##STR00016##
To a dry round-bottom flask under nitrogen were added sodium
hydride (60% dispersion in oil, 0.018 g, 0.45 mmol) and
tetrahydrofuran (THF, 2.1 mL), followed by MeOH (0.018 mL, 0.45
mmol). The reaction was allowed to stir at room temperature until
cessation of hydrogen evolution was observed (45 min). The reaction
was then cooled to a temperature of 0.degree. C., and
S-(1-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxop-
ropan-2-yl) ethanethioate (0.150 g, 0.425 mmol) in THF (2.1 mL) was
added. The reaction was warmed to room temperature and stirred for
30 minutes. The reaction was again cooled to a temperature of about
0.degree. C., and 1,1,1-trifluoro-2-iodoethane (0.063 mL, 0.64
mmol) in THF (2.1 mL) was added. The reaction was warmed to room
temperature and stirred overnight. The reaction was diluted in
ethyl acetate (EtOAc, 20 mL) and quenched with water (5 mL). The
layers were separated, and the aqueous layer was extracted with
EtOAc (3.times.10 mL). The combined organic extracts were dried
over Na.sub.2SO.sub.4, filtered, and concentrated under reduced
pressure to give yellow oil. The crude product was purified via
flash chromatography (SiO.sub.2) eluting with 0%-75%
EtOAc/CH.sub.2Cl.sub.2 to give the title molecule C4 as opaque,
viscous oil (0.043 g, 25%). IR (thin film) 1657 cm.sup.-1; .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.96 (d, J=2.6 Hz, 1H), 8.64 (dd,
J=4.8, 1.4 Hz, 1H), 8.14-7.96 (m, 2H), 7.47 (dd, J=8.3, 4.8 Hz,
1H), 3.82 (s, 1H), 3.59 (s, 1H), 3.44 (s, 1H), 3.25 (qd, J=10.2,
3.8 Hz, 2H), 1.48 (d, J=6.8 Hz, 3H), 1.17 (t, J=7.2 Hz, 3H);
.sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -66.16; ESIMS m/z 393
([M+H].sup.+).
Example 4
Preparation of
3-(4-(N-ethyl-2-methyl-3-(methylsulfonyl)propanamido)-3-methyl-1H-pyrazol-
-1-yl)pyridine-1-oxide
Compound F4
##STR00017##
To a solution of
N-ethyl-2-methyl-N-(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(methylt-
hio)propanamide (prepared as described in the PCT Publication No.
WO 2013/062981) (0.12 g, 0.38 mmol) in AcOH (1 mL) was added sodium
perborate tetrahydrate (0.13 g, 0.83 mmol) and heated at a
temperature of about 60.degree. C. for one hour. The reaction was
quenched with saturated aqueous NaHCO.sub.3, extracted with EtOAc,
and concentrated under reduced pressure. Purification by flash
chromatography (SiO.sub.2) eluting with 0%-15%
MeOH/CH.sub.2Cl.sub.2 afforded the title compound F4 as clear oil
(0.014 g, 10%).
The following molecules were made in accordance with the procedures
disclosed in Example 4:
##STR00018##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-(methylsulfonyl)propanamido)-1H-pyrazol-
-1-yl) 1-oxide (Compound F12) was obtained from
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methyl-3-(methylt-
hio)propanamide (prepared as described in the U.S. Publication No.
2012/0110702) and isolated as clear oil (0.009 g, 10%).
##STR00019##
3-(3-Chloro-4-(N-ethyl-2-((2,2,2-trifluoroethyl)sulfonyl)propanamido)-1H--
pyrazol-1-yl)pyridine 1-oxide (Compound F8) was isolated as a white
solid (0.0099 g, 8%).
##STR00020##
3-(3-Chloro-4-(N-ethyl-2-((2,2,2-trifluoroethyl)sulfinyl)propanamido)-1H--
pyrazol-1-yl)pyridine 1-oxide (Compound F7) was isolated as a white
solid (0.0104 g, 9%).
##STR00021##
3-(3-chloro-4-(N-ethyl-2-(methylsulfonyl)acetamido)-1H-pyrazol-1-yl)pyrid-
ine 1-oxide (Compound FA11) was isolated as a white semi-solid
(0.077 g, 25%).
##STR00022##
3-(3-chloro-4-(N-methyl-2-(methylsulfonyl)propanamido)-1H-pyrazol-1-yl)py-
ridine 1-oxide (Compound FAl2) was isolated as a off-white
semi-slid (0.1 g, 27%).
##STR00023##
3-(3-chloro-4-(N-ethyl-2-(methylsulfonyl)propanamido)-1H-pyrazol-1-yl)pyr-
idine 1-oxide (Compound FA13) was isolated as a white semi-solid
(0.092 g, 15%).
##STR00024##
3-(3-chloro-4-(N-(cyclopropylmethyl)-2-(methylsulfonyl)propanamido)-1H-py-
razol-1-yl)pyridine 1-oxide (Compound FA14) was isolated as a
yellow semi-solid (0.096 g, 16%).
Example 5
Preparation of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-mercatopropanamid-
e
Compound C6
##STR00025##
To a solution of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(tritylthio)propa-
namide (0.169 g, 0.306 mmol) in CH.sub.2Cl.sub.2 (3 mL) were added
triethylsilane (0.244 mL, 1.53 mmol) and TFA (0.235 mL, 3.06 mmol),
sequentially. The reaction was stirred overnight at room
temperature. The reaction mixture was diluted with CH.sub.2Cl.sub.2
(10 mL) and carefully poured into a separatory funnel containing
saturated aqueous NaHCO.sub.3 (10 mL). The layers were mixed and
then separated. The aqueous phase was extracted with
CH.sub.2Cl.sub.2 (3.times.10 mL), and the combined organic extracts
were dried over Na.sub.2SO.sub.4, filtered, and concentrated under
reduced pressure. Purification by flash chromatography (SiO.sub.2)
eluting with 0%-100% EtOAc/CH.sub.2Cl.sub.2 afforded the title
compound C6 as a white solid (0.086 g, 86%). .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.96 (dd, J=2.7, 0.7 Hz, 1H), 8.63 (dd, J=4.8,
1.5 Hz, 1H), 8.06 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.97 (s, 1H), 7.47
(ddd, J=8.4, 4.8, 0.8 Hz, 1H), 3.72 (1, J=7.2 Hz, 2H), 2.79 (dt,
J=8.4, 6.7 Hz, 2H), 2.49 (t, J=6.7 Hz, 2H), 1.67 (t, J=8.4 Hz, 1H),
1.17 (t, J=7.2 Hz, 3H); ESIMS m/z 311 ([M+H].sup.+).
Example 6
Preparation of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluorocyclopropy-
l)methyl)thio)-N-ethylpropanamide
Compound C7
##STR00026##
To a solution of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-mercatopropanamid-
e (0.10 g, 0.32 mmol) in THF (1 mL) was added sodium hydride (60%
dispersion in oil, 0.014 g, 0.34 mmol). The resulting mixture was
stirred at room temperature for 10 minutes, followed by addition of
2-(bromomethyl)-1,1-difluorocyclopropane (0.060 g, 0.35 mmol). The
mixture was stirred at room temperature for 24 hours and diluted
with saturated aqueous ammonium chloride (NH.sub.4Cl) and EtOAc.
The organic phase was separated, and the aqueous phase extracted
with EtOAc (2.times.50 mL). The combined organic extracts were
dried over magnesium sulfate (MgSO.sub.4), filtered, and
concentrated under reduced pressure to give colorless oil. This oil
was purified by flash chromatography (SiO.sub.2) eluting with a
mixture of EtOAc and hexanes to give the title molecule C7 as a
colorless gum (0.10 g, 78%). IR (thin film) 3092, 2975, 2931, 1659,
1584 cm.sup.-1; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.99-8.90
(m, 1H), 8.63 (dd, J=4.8, 1.5 Hz, 1H), 8.05 (ddd, J=8.3, 2.7, 1.5
Hz, 1H), 7.96 (s, 1H), 7.47 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 3.72 (q,
J=7.2 Hz, 2H), 2.87 (t, J=7.3 Hz, 2H), 2.63-2.55 (m, 2H), 2.46 (t,
J=7.3 Hz, 2H), 1.76 (ddq, J=13.2, 11.4, 7.5 Hz, 1H), 1.48 (dddd,
J=12.3, 11.2, 7.8, 4.5 Hz, 1H), 1.17 (t, J=7.2 Hz, 3H), 1.04 (dtd,
J=13.2, 7.6, 3.7 Hz, 1H); ESIMS m/z 400 ([M+H].sup.+).
Example 7
Preparation of
3(3-chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)sulfonyl-N-ethylpropana-
mide)-1H-pyrazol-1-yl)pyridine 1-oxide
Compound F11
##STR00027##
To a solution of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluorocyclopropy-
l)methyl)thio)-N-ethylpropanamide (0.177 g, 0.422 mmol) in
CH.sub.2Cl.sub.2 (5 mL) was added 3-chloroperoxybenzoic acid
(m-CPBA, 77%, 0.435 g, 1.77 mmol) and stirred at room temperature
for one hour. The reaction mixture was diluted with
CH.sub.2Cl.sub.2 and washed with saturated aqueous NH.sub.4Cl and
brine, dried over MgSO.sub.4, and concentrated under reduced
pressure. Purification by flash chromatography (SiO.sub.2) eluting
with CH.sub.2Cl.sub.2 and MeOH afforded the title compound F11 as
an off-white solid (0.157 g, 79%).
The following compounds in Table 5 may be prepared according to the
procedures disclosed in Example 7:
P3, P6, P11, P14, P17, P20, P23, P26, P29, P35, P38, P41, P44, P47,
P52, P55, P58, P61, P64, P67, P70, P73, P76, P79, P82, P85, P88,
P91, P94, P97, P100, P103, P106, P109.
Example 8
Preparation of 3-((3,3,3-trifluoropropyl)thio)propanoyl
chloride
Compound C8
##STR00028##
A dry 5-liter round bottom flask equipped with magnetic stirrer,
nitrogen inlet, reflux condenser, and thermometer, was charged with
3-((3,3,3-trifluoropropyl)thio)propanoic acid (prepared as
described in the PCT Publication No. WO 2012/062981) (188 g, 883
mmol) in CH.sub.2Cl.sub.2 (3 L). Thionyl chloride (525 g, 321 mL,
4.42 mol) was then added dropwise over 50 minutes. The reaction
mixture was heated to reflux for two hours, then cooled to room
temperature. Concentration under reduced pressure on a rotary
evaporator, followed by distillation (40 Torr, product collected a
temperature of from about 123.degree. C. to about 127.degree. C.)
gave the title compound C8 as clear colorless liquid (177 g, 86%).
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 3.20 (t, J=7.1 Hz, 2H),
2.86 (t, J=7.1 Hz, 2H), 2.78-2.67 (m, 2H), 2.48-2.31 (m, 2H).
Example 9
Preparation of
3-(3-chloro-4-(N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamido)-1H-pyr-
azol-1-yl)pyridine 1-oxide
Compound F5
##STR00029##
To a solution of
3-(3-chloro-4-(ethylamino)-1H-pyrazol-1-yl)pyridine 1-oxide (0.23
g, 0.98 mmol) in CH.sub.2Cl.sub.2 (10 mL) at a temperature of about
0.degree. C. were added DIPEA (0.26 mL, 1.5 mmol), DMAP (0.012 g,
0.098 mmol), and 3-((3,3,3-trifluoropropyl)thio)propanoyl chloride
(0.24 g, 1.1 mmol) sequentially. The reaction was warmed to room
temperature and stirred for 4 hours. The reaction was quenched with
water (10 mL) and vigorously stirred for 5 minutes. The phases were
separated, and the aqueous phase was extracted with
CH.sub.2Cl.sub.2 (3.times.10 mL). The combined organic extracts
were dried over Na.sub.2SO.sub.4, filtered and concentrated under
reduced pressure. Purification by reverse phase flash
chromatography eluting with 0%-100% acetonitrile (MeCN)/water
afforded the title compound F5 as orange oil (0.197 g, 45%).
The following molecules were made in accordance with the procedures
disclosed in Example 9:
##STR00030##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-(methylthio)propajamido)-1H-pyrazol-1-y-
l)pyridine 1-oxide (Compound F10) was obtained from
2-methyl-3-(methylthio)propanoyl chloride (prepared as described in
the U.S. Publication NO. 2012/0053146) and isolated as orange oil
(0.299 g, 66%).
##STR00031##
3-(3-Chloro-4-(N-ethyl-3-(methylthio)propanamido)-1H-pyrazol-1-yl)
pyridine 1-oxide (Compound F2) was obtained from
3-methylthiopropionyl chloride and isolated as a white solid (0.251
g, 53%).
The following compounds in TABLE 5 may be prepared according to the
procedures disclosed in Example 9:
P1, P4, P7, P9, P12, P15, P18, P21, P24, P32, P36, P39, P42, P45,
P48, P50, P53, P56, P59, P62, P65, P68, P71, P74, P77, P80, P92,
P95, P98, P101, P104, P107
Example 10
Preparation of
3-(3-chloro-4-(N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamido)-1H-
-pyrazol-1-yl)pyridine 1-oxide
Compound F1
##STR00032##
To a solution of 3-(3-chloro-4-(N-ethyl-3-((3,3,3
trifluoropropyl)thio) propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide
(0.095 g, 0.225 mmol) in MeOH (1.1 mL) at room temperature was
added a 30% aqueous solution of H.sub.2O.sub.2 (0.069 mL, 0.67
mmol). The reaction was stirred at room temperature overnight for
18 hours. The reaction was concentrated under reduced pressure,
diluted with CH.sub.2Cl.sub.2 (1 mL) and MeOH (1 mL), and
concentrated under reduced pressure. Purification by reverse phase
flash chromatography eluting with 0%-100% MeCN/water afforded the
title compound F1 as a white semi-solid (0.081 g, 78%).
The following molecules were made in accordance with the procedures
disclosed in Example 10:
##STR00033##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-(methylsulfinyl)propanamido-1H-pyrazol--
1-yl)pyridine 1-oxide (Compound F6) was isolated as a clear
semi-solid (0.092 g, 84%).
##STR00034##
3-(3-Chloro-4-(N-ethyl-3-(methylsulfinyl)propanamido)-1H-pyrazol-1-yl)
pyridine 1-oxide (Compound F9) was isolated as a clear semi-solid
(0.093 g, 87%).
The following compounds in Table 4 may be prepared according to the
procedures disclosed in Example 10:
P2, P5, P8, P10, P13, P16, P19, P22, P25, P28, P31, P34, P37, P40,
P43, P46, P49, P51, P54, P57, P60, P63, P66, P72, P75, P78, P81,
P84, P87, P90, P93, P96, P99, P102, P105, P108.
Example 11
Preparation of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoro-
propyl)thio)propanamide
Compound C9
##STR00035##
To a solution of
3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (prepared as
described in the PCT Publication No. WO 2013/062981) (10 g, 44.9
mmol) in CH.sub.2Cl.sub.2 (100 mL) at a temperature of about
0.degree. C. and under N.sub.2 were added pyridine (5.45 mL, 67.4
mmol), 4-dimethylaminopyridine (DMAP) (2.74 g, 22.45 mmol), and
3-((3,3,3-trifluoropropyl)thio)propanoyl chloride (9.91 g, 44.9
mmol), sequentially. The reaction was warmed to ambient temperature
and stirred for one hour. The reaction was poured into water (100
mL) and the resulting mixture was stirred for 5 min. The mixture
was transferred to a separatory funnel and the layers were
separated. The aqueous phase was extracted with CH.sub.2Cl.sub.2
(3.times.50 mL) and the combined organic extracts were dried over
Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The crude
product was purified via normal phase flash chromatography (0 to
100% EtOAc/CH.sub.2Cl.sub.2) to afford the desired product as a
pale yellow solid (17.21 g, 89%).
Example 12
Preparation of
3-(3-chloro-4-(N-ethyl-3-((3,3,3-trifluoropropyl)sulfonyl)propanamido)-1H-
-pyrazol-1-yl)pyridine 1-oxide
Compound F13
##STR00036##
To a solution of
N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoro-
propyl)thio)propanamide (0.203 g, 0.499 mmol) in AcOH (5 mL) at
room temperature was added sodium perborate, tetrahydrate (0.230 g,
1.50 mmol). The mixture was warmed to a temperature of 55.degree.
C. and stirred for 5 hours. The reaction was cooled to room
temperature and carefully diluted with saturated aqueous
NaHCO.sub.3 (5 mL) and EtOAc (10 mL). The layers were separated,
and the aqueous layer was extracted with EtOAc (3.times.10 mL). The
combined organic extracts were washed with brine, dried over
Na.sub.2SO.sub.4, filtered, and concentrated under reduced
pressure. Purification by flash chromatography (SiO.sub.2) eluting
with 0%-30% MeOH/EtOAc afforded the title compound F13 as a white
solid (0.129 g, 54%).
Example 13
Prophetic preparation of
3-(3-chloro-4-(N-ethyl-3-((3,3,3trifluoropropyl)thio)propanethioamido)-1H-
-pyrazol-1-yl)pyridine 1-oxide
Compound P27
##STR00037##
To a solution of 3-(3-chloro-4-(N-ethyl-3-((3,3,3
trifluoropropyl)thio) propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide
(1 equivalent (eq)) in a solvent, such as toluene, (at a
concentration between about 0.01 M to about 1 M) at ambient
temperature may be added a thionating reagent, such as Lawesson's
reagent (from about 0.5 eq to about 1 eq). The reaction may be
capped in a microwave vial and heated at a temperature from about
100.degree. C. to about 150.degree. C. for from about 15 minutes to
about 90 minutes in a BIOTAGE INITIATOR.RTM. microwave reactor with
external IR-sensor temperature monitoring from the side of the
vessel. The product may be then obtained using standard organic
chemistry techniques or workup and purification.
The following compounds in TABLE 5 may be prepared according to the
procedures disclosed in Example 13: P30, P33, P83, P86, P89.
Example 14
Preparation of
3-(3-chloro-4-(N-methyl-3-((3,3,3-trifluoropropyl)thio)propanamido)-1H-py-
razol-1-yl)pyridine 1-oxide
Compound P1
##STR00038##
A stirred suspension of
3-(3-chloro-4-(methylamino)-1H-pyrazol-1-yl)pyridine 1-oxide (0.15
g, 0.66 mmol) in THF (10 mL) was charged with DMAP (0.33 mmol) and
34(3,3,3-trifluoropropyl)thio)propanoyl chloride (0.32 g, 1.5 mmol)
at room temperature. The reaction mixture was stirred at room
temperature for 2 hours. The reaction mixture was diluted with
water (20 mL) and was extracted with EtOAc (2.times.25 mL). The
combined organic layer was washed with a saturated NaHCO.sub.3
solution (2.times.20 mL) and brine (2.times.20 mL). The separated
organic layer was dried over solid Na.sub.2SO.sub.4, filtered, and
concentrated. The crude residue was purified by flash column
chromatography using 0-10% MeOH/CH.sub.2Cl.sub.2 as eluent provide
the title compound (0.20 g, 75%).
The following molecules were made in accordance with the procedures
disclosed in Example 14:
##STR00039##
3-(3-Chloro-4-(N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanam-
ido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P9) was isolated
(0.21 g, 72%).
##STR00040##
3-(4-(N-Ethyl-3-((3,3,3-trilluoropropyl)thio)propanamido)-3-methyl-1H-pyr-
azol-1-yl)pyridine 1-oxide (Compound P18) was isolated (0.053 g,
20%)
##STR00041##
3-(3-Chloro-4-(N-ethyl-3-((3,3,3-trilluoropropyl)thio)propanamido)-1H-pyr-
azol-1-yl)-5-fluoropyridine 1-oxide (Compound P36) was isolated
(0.13 g, 43%).
##STR00042##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)thio)-N-ethylpropanami-
do)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P48) was isolated
(0.16 g, 58%).
##STR00043##
3-(3-Chloro-4-(N-ethyl-3-((4,4,4-trifluorobutyl)thio)propanamido)-1H-pyra-
zol-1-yl)pyridine 1-oxide (Compound P53) was isolated (0.22 g,
77%).
##STR00044##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)thio)-N-methylpropanam-
ido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P56) was isolated
(0.22 g, 81%).
##STR00045##
3-(3-Chloro-4-(N-methyl-3-((4,4,4-trifluorobutyl)thio)propanamido)-1H-pyr-
azol-1-yl)pyridine 1-oxide (Compound P62) was isolated (0.18 g,
64%).
##STR00046##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)thio)-N-(prop-2-yn-1-y-
l)propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P65) was
isolated (0.24 g, 84%).
##STR00047##
3-(3-Chloro-4-(N-(prop-2-yn-1-yl)-3-((4,4,4-trifluorobutyl)thio)propanami-
do)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P71) was isolated
(0.16 g, 55%).
##STR00048##
3-(4-(3-(((2,2-Difluorocyclopropyl)methyl)thio)-N-ethylpropanamido)-3-met-
hyl-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P74) was isolated
(0.19 g, 73%).
##STR00049##
3-(4-(N-Ethyl-3-((4,4,4-trifluorobutyl)thio)propanamido)-3-methyl-1H-pyra-
zol-1-yl)pyridine 1-oxide (Compound P80) was isolated (0.13 g,
49%).
##STR00050##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)thio)-N-ethylpropanami-
do)-1H-pyrazol-1-yl)-5-fluoropyridine 1-oxide (Compound P92) was
isolated (0.20 g, 70%).
##STR00051##
3-(3-Chloro-4-(N-ethyl-3-((4,4,4-trilluorobutyl)thio)propanamido)-1H-pyra-
zol-1-yl)-5-fluoropyridine 1-oxide (Compound P98) was isolated
(0.23 g, 75%).
##STR00052##
3-(4-(N-Ethyl-2-methyl-3-((3,3,3-trilluoropropyl)thio)propanamido)-3-meth-
yl-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA1) was isolated
(0.036 g, 13%).
##STR00053##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-((3,3,3-trifluoropropyl)thio)
propanamido)-1H-pyrazol-1-yl)-5-fluoropyridine 1-oxide (Compound
FA2) was isolated (0.093 g, 31%).
##STR00054##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-((3,3,3-trifluoropropyl)thio)propanamid-
o)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA3) was isolated
(0.092 g, 32%).
##STR00055##
3-(3-Chloro-4-(2-methyl-N-(prop-2-yn-1-yl)-3-((3,3,3trifluoropropyl)thio)-
propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA4) was
isolated (0.097 g, 33%).
##STR00056##
3-(3-Chloro-4-(N,2-dimethyl-3-((3,3,3-trifluoropropyl)thio)propanamido)-1-
H-pyrazol-1-yl)pyridine 1-oxide (Compound FA5) was isolated (0.061
g, 22%).
Example 15
Preparation of
3-(3-chloro-4-(N-methyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamido)-1-
H-pyrazol-1-yl)pyridine 1-oxide
Compound P2
##STR00057##
A stirred suspension of
3-(3-chloro-4-(N-methyl-3-(3,3,3-trifluoropropyl)thio)propanamido)-1H-pyr-
azol-1-yl)pyridine 1-oxide (0.14 g, 0.35 mmol) in acetic acid (4.0
mL) was charged with sodium perborate tetrahydrate (0.058 g, 0.38
mmol) at room temperature. The reaction mixture was stirred at room
temperature for 4 hours. The reaction mixture was diluted with
EtOAc (20 mL), quenched with a saturated NaHCO.sub.3 solution (100
mL) slowly and the layers were separated. The aqueous layer was
extracted with EtOAc (2.times.25 mL). The combined organic layer
was washed with brine (2.times.20 mL) and was dried over solid
Na.sub.2SO.sub.4, filtered, and concentrated. The crude residue was
purified by flash column chromatography using 0-10%
MeOH/CH.sub.2Cl.sub.2 to provide the title compound (0.079 g,
53%)
The following molecules were made in accordance with the procedures
disclosed in Example 15
##STR00058##
3-(3-chloro-4-(N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulfinyl)prop-
anamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P10) was
isolated (0.075 g, 48%).
##STR00059##
3-(4-(N-Ethyl-3-((3,3,3-trilluoropropyl)sulfinyl)propanamido)-3-methyl-1H-
-pyrazol-1-yl)pyridine 1-oxide (Compound P19) was isolated (0.091
g, 62%).
##STR00060##
3-(3-Chloro-4-(N-ethyl-3-((3,3,3-trilluoropropyl)sulfinyl)propanamido)-1H-
-pyrazol-1-yl)-5-fluoropyridine 1-oxide (Compound P37) was isolated
(0.11 g, 71%).
##STR00061##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)sulfinyl)-N-ethylpropa-
namido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P49) was
isolated (0.076 g, 50%).
##STR00062##
3-(3-Chloro-4-(N-ethyl-3-((4,4,4-trilluorobutyl)sulfinyl)propanamido)-1H--
pyrazol-1-yl)pyridine 1-oxide (Compound P54) was isolated (0.082 g,
52%).
##STR00063##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)sulfinyl)-N-methyl
propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P57) was
isolated (0.075 g, 51%).
##STR00064##
3-(3-Chloro-4-(N-methyl-3-((4,4,4-trifluorobutyl)sulfinyl)propanamido)-1H-
-pyrazol-1-yl)pyridine 1-oxide (Compound P63) was isolated (0.071
g, 46%).
##STR00065##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)sulfinyl)-N-(prop-2-yn-
-1-yl)propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P66)
was isolated (0.074 g, 48%).
##STR00066##
3-(3-Chloro-4-(N-(prop-2-yn-1-yl)-3-((4,4,4-trifluorobutyl)sulfinyl)
propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P72) was
isolated (0.097 g, 42%).
##STR00067##
3-(4-(3-(((2,2-Difluorocyclopropyl)methyl)sulfinyl)-N-ethylpropan-amido)--
3-methyl-1H-pyrazol-1-yl)pyridine 1-oxide (Compound P75) was
isolated (0.10 g, 72%).
##STR00068##
3-(4-(N-Ethyl-3-((4,4,4-trilluorobutyl)sulfinyl)propanamido)-3-methyl-1H--
pyrazol-1-yl)pyridine 1-oxide (Compound P81) was isolated (0.094 g,
62%).
##STR00069##
3-(3-Chloro-4-(3-(((2,2-difluorocyclopropyl)methyl)sulfinyl)-N-ethylpropa-
namido)-1H-pyrazol-1-yl)-5-fluoropyridine 1-oxide (Compound P93)
was isolated (0.10 g, 64%).
##STR00070##
3-(3-Chloro-4-(N-ethyl-3-((4,4,4-trilluorobutyl)sulfinyl)propanamido)-1H--
pyrazol-1-yl)-5-fluoropyridine 1-oxide (Compound P99) was isolated
(0.074 g, 45%).
##STR00071##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-((3,3,3-trifluoropropyl)sulfinyl)
propanamido)-1H-pyrazol-1-yl)-5-fluoropyridine 1-oxide (Compound
FA6) was isolated (0.073 g, 44%)
##STR00072##
3-(3-Chloro-4-(2-methyl-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)sulf-
inyl)propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA7)
was isolated (0.13 g, 80%).
##STR00073##
3-(3-Chloro-4-(N,2-dimethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamid-
o)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA8) was isolated
(0.074 g, 48%).
##STR00074##
3-(3-Chloro-4-(N-ethyl-2-methyl-3-((3,3,3-trifluoropropyl)sulfinyl)
propanamido)-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA9) was
isolated (0.13 g, 82%).
##STR00075##
3-(4-(N-Ethyl-2-methyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamido)-3--
methyl-1H-pyrazol-1-yl)pyridine 1-oxide (Compound FA10) was
isolated (0.11 g, 75%).
Example 16
Preparation of
3-(3-chloro-4-(N-ethyl-3-((2,2,2-trifluoroethyl)thio)propanamido)-1H-pyra-
zol-1-yl)pyridine 1-oxide
Compound P50
##STR00076##
To a suspension of 3-((2,2,2-trifluoroethyl)thio)propanoic acid
(0.296 g, 1.57 mmol) in 1,2-dichloroethane (DCE, 10.5 mL) was added
oxalyl chloride (0.160 mL, 1.83 mmol) and one drop of DMF. The acid
failed to go completely into solution and DMF (0.5 mL) was added.
The reaction was stirred for 1 hour and then concentrated. The
residue was taken up in DCE (5 mL) and transferred to a flask
(under N.sub.2, at room temperature) containing
3-(3-chloro-4-(ethylamino)-1H-pyrazol-1-yl)pyridine 1-oxide (0.250
g, 1.05 mmol) and DMAP (0.384 g, 3.14 mmol) in DCE (6 mL). The
reaction was left to stir overnight. The reaction was diluted in
CH.sub.2Cl.sub.2 (10 mL) and quenched with water (10 mL). The
phases were mixed and then separated. The organic phase was washed
with brine (2.times.10 mL) and then dried over Na.sub.2SO.sub.4,
filtered, and concentrated. The resulting residue was purified via
flash column chromatography using 0-30% MeOH/EtOAc as eluent
followed by reverse phase flash column chromatography using 5-100%
MeCN/water as eluent to afford the desired product as a white solid
(0.044 g, 10%).
Example 17
Preparation of
3-(4-((tert-butoxycarbonyl)(prop-2-yn-1-yl)amino)-3-chloro-1H-pyrazol-1-y-
l)pyridine 1-oxide
Compound CA5
##STR00077##
A stirred solution of tent-butyl
(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(prop-2-yn-1-yl)carbamate
(1.18 g, 3.57 mmol) (WO 2013/062981) in CH.sub.2Cl.sub.2 (25 mL)
was charged with m-CPBA (0.861 g, 4.99 mmol) portionwise over 5
minutes at 0.degree. C. under a N.sub.2 atmosphere. The reaction
mixture was stirred at room temperature for 16 hours. The reaction
mixture was concentrated. The crude residue was purified by flash
column chromatography using 0-20% MeOH/EtOAc as eluent to afford
the title compound (1.18 g, 95%): .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.65 (s, 1H), 8.14 (d, J=6.4 Hz, 1H), 8.01 (s, 1H), 7.59
(d, J=8.0 Hz, 1H), 7.36 (dd, J=8.0, 6.4 Hz, 1H), 4.34 (d, J=1.6 Hz,
2H), 2.30 (t, J=1.6 Hz, 1H), 1.46 (s, 9H); ESIMS m/z 349
([M+H].sup.+).
The following molecules were made in accordance with the procedures
disclosed in Example 17:
##STR00078##
3-(4-((tert-Butoxycarbonyl)(ethyl)amino)-3-methyl-1H-pyrazol-1-yl)pyridin-
e 1-oxide (Compound CA6) was isolated as an off-white solid from
tert-butyl
ethyl(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (US
2012/0110702) (9.00 g, 85%): .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.68 (s, 1H), 8.08 (dd, J=8.4, 1.2 Hz, 1H), 7.74 (s, 1H),
7.56 (dd, J=8.4, 1.2 Hz, 1H), 7.31 (d, J=8.4, 1H), 3.56 (q, J=7.2
Hz, 2H), 2.22 (s, 3H), 1.44 (s, 9H), 1.14 (t, J=7.2 Hz, 3H); ESIMS
m/z 319 ([M+H].sup.+).
##STR00079##
3-(4-((tert-Butoxycarbonyl)(methyl)amino)-3-chloro-1H-pyrazol-1-yl)pyridi-
ne 1-oxide (Compound CA7) was isolated from
tert-butyl(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate
(US 2012/0110702) (1.10 g, 95%): .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.63 (s, 1H), 8.12 (d, J=6.4 Hz, 1H), 7.81 (s, 1H), 7.55
(d, J=8.0 Hz, 1H), 7.34 (dd, J=8.0, 6.4 Hz, 1H), 3.21 (s, 3H), 1.45
(s, 9H); ESIMS m/z 325 ([M+H].sup.+).
##STR00080##
3-(4-((tert-Butoxycarbonyl)(ethyl)amino)-3-chloro-1H-pyrazol-1-yl)-5-fluo-
ropyridine1-oxide (Compound CA8) was isolated as an off-white solid
from
tert-butyl(3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)carba-
mate (US 2012/0110702) (2.80 g, 100%): .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.59 (s, 1H), 8.09 (t, J=2.0, 1.6 Hz, 1H), 7.86
(s, 1H), 7.48 (dd, J=8.4, 1.6 Hz, 1H), 3.60 (q, J=7.2 Hz, 2H), 1.45
(bs, 9H), 1.17 (t, J=7.2 Hz, 3H); ESIMS m/z 357 ([M+H].sup.+).
Example 18
Preparation of 3-((4,4,4-trifluorobutyl)thio)propanoic acid
Compound CA9
##STR00081##
A stirred solution of 3-mercaptopropanoic acid (12.2 g, 37.6 mmol)
in EtOH (40 mL) was charged with sodium hydroxide (3.31 g, 82.9
mmol) followed by addition of (10.8 g, 56.5 mmol) at room
temperature. The reaction mixture was heated to reflux for 2 hours.
The reaction mixture was concentrated. The obtained crude compound
was diluted with water (50 mL) and was washed with methy
tert-butylether (2.times.20 mL). The aqueous layer was acidified to
pH .about.2 with a hydrochloric acid solution (2 N) and was
extracted with EtOAc (2.times.100 mL). The combined organic layer
was washed with brine (1.times.20 mL) and was dried over anhydrous
Na.sub.2SO.sub.4, filetered, and concentrated to afford the title
compound as a colorless liquid (5.77 g, 71%): .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 10.0 (bs, 1H), 2.79 (dt, J=8.0, 0.8 Hz, 2H),
2.68-2.60 (m, 4H), 2.28-2.10 (m, 2H), 1.90-1.83 (m, 2H).
The following molecules were made in accordance with the procedures
disclosed in Example 18:
##STR00082##
2-Methyl-3-((3,3,3-trifluoropropyl)thio)propanoic acid (Compound
CA10) was isolated as a colorless liquid (6.10 g, 75%): .sup.1H NMR
(300 MHz, CDCl.sub.3): .delta. 2.95-2.85 (m, 1H), 2.76-2.41 (m,
4H), 2.43-2.34 (m, 2H), 1.31 (d, J=8.4 Hz, 3H).
Example 19
Preparation of 3-((4,4,4-trifluorobutyl)thio)propanoyl chloride
Compound CA11
##STR00083##
A stirred solution of 3-(4,4,4-trifluorobutyl)thio)propanoic acid
(1.50 g, 6.94 mmol) in CH.sub.2Cl.sub.2 (10 mL) was charged with
oxalyl chloride (1.32 g, 10.4 mmol) dropwise at 0.degree. C.,
followed by DMF (catalytic) and was stirred at room temperature for
2 hours. The reaction mixture was concentrated to afford the title
compound as a liquid (1.62 g, 100%). The obtained acid chloride was
directly used without characterization.
The following molecules were made in accordance with the procedures
disclosed in Example 19:
##STR00084##
2-Methyl-3-((3,3,3-trifluoropropyl)thio)propanoyl chloride
(Compound CA12) was isolated as a liquid (1.62 g, 100%). The
obtained acid chloride was directly used without
characterization.
TABLE 3 shows non-limiting examples of the
1-(3-pyridyl-N-oxide)pyrazole compounds of formula I, II, or III,
or any agriculturally acceptable salt thereof. Compounds F1, F6,
and F9 were prepared according to Example 10. Compounds F2, F5, and
F10 were prepared according to Example 9. Compounds F4, F7, F8,
F12, FAH, FAl2, FA13, and FA14 were prepared according to Example
4. Compound F11 was prepared according to Example 7. Compound F13
was prepared according to Example 12. Compounds P1, P9, P18, P36,
P48, P53, P56, P62, P65, P71, P74, P80, P92, P98, FA1, FA2, FA3,
FA4, and FA5 were prepared according to Example 14. Compounds P2,
P10, P19, P37, P49, P54, P57, P63, P66, P72, P75, P81, P93, P99,
FA6, FA7, FA8, FA9, and FA10 were prepared according to Example 15.
Compound P50 was prepared according to Example 16.
TABLE 4 and TABLE 5 show further non-limiting examples of the
1-(3-pyridyl-N-oxide)pyrazole compounds of formula I, II, or III,
or any agriculturally acceptable salt thereof.
TABLE-US-00003 TABLE 3 Appear- ance ESIMS .sup.13C NMR, No.
Structure mp (.degree. C.) (m/z) .sup.1H NMR .sup.19F NMR, IR F1
##STR00085## White Semi- Solid 439 ([M + H].sup.+) (400 MHz,
CDCl.sub.3) .delta. 8.73 (t, J = 1.8 Hz, 1H), 8.17 (ddd, J = 6.5,
1.7, 0.9 Hz, 1H), 8.02 (s, 1H), 7.56 (ddd, J = 8.5, 2.1, 0.9 Hz,
1H), 7.38 (dd, J = 8.5, 6.4 Hz, 1H), 3.72 (p, J = 7.0 Hz, 2H), 3.17
(dt, J = 13.1, 7.6 Hz, 1H), 3.03-2.79 (m, 3H), 2.74-2.49 (m, 4H),
1.16 (t, J = 7.2 Hz, 3H) .sup.19F NMR (376 MHz, CDCl.sub.3) .delta.
-65.8 F2 ##STR00086## White Solid mp = 163-165 341 ([M + H].sup.+)
(400 MHz, CDCl.sub.3) .delta. 8.88 (t, J = 1.8 Hz, 1H), 8.18 (ddd,
J = 6.4, 1.7, 0.9 Hz, 1H), 8.11 (s, 1H), 7.65 (ddd, J = 8.5, 2.0,
0.9 Hz, 1H), 7.41 (dd, J = 8.5, 6.4 Hz, 1H), 3.71 (q, J = 7.2 Hz,
2H), 2.79 (dd, J = 7.8, 6.9 Hz, 2H), 2.43 (t, J = 7.4 Hz, 2H), 2.07
(s, 3H), 1.16 (t, J = 7.2 Hz, 3H) .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 171.3, 142.0, 138.4, 137.5, 130.6, 126.9,
126.2, 124.8, 115.0, 43.9, 34.0, 29.6, 15.9, 13.1 F4 ##STR00087##
Clear Oil (400 MHz, CDCl.sub.3) .delta. 8.77 (s, 1H), 8.12 (dd, J =
6.4, 0.7 Hz, 1H), 8.08 (s, 1H), 7.55 (d, J = 8.2 Hz, 1H), 7.34 (dd,
J = 8.4, 6.5 Hz, 1H), 4.14 (s, 0.5H), 3.82 (dd, J = 13.5, 11.0 Hz,
1H), 3.42-3.09 (m, 1.5H), 3.09-2.90 (m, 4H), 2.86 (dd, J = 13.6,
2.4 Hz, 1H), 2.30 (s, 3H), 1.21-1.08 (m, 6H) IR (thin film): 1654
cm.sup.-1 F5 ##STR00088## Orange Oil 423 ([M + H].sup.+) (400 MHz,
CDCl.sub.3) .delta. 8.88 (t, J = 1.8 Hz, 1H), 8.18 (ddd, J = 6.4,
1.7, 0.9 Hz, 1H), 8.08 (s, 1H), 7.65 (ddd, J = 8.5, 2.1, 0.9 Hz,
1H), 7.41 (dd, J = 8.5, 6.5 Hz, 1H), 3.71 (q, J = 7.1 Hz, 2H), 2.84
(t, J = 7.2 Hz, 2H), 2.72- 2.60 (m, 2H), 2.51-2.29 (m, 4H), 1.16
(t, J = 7.2 Hz, 3H) .sup.19F NMR (376 MHz, CDCl.sub.3) .delta.
-66.4 F6 ##STR00089## Clear Semi- Solid 371 ([M + H].sup.+) .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.77 (t, J = 1.8 Hz, 0.5H), 8.74
(t, J = 1.8 Hz, 0.5H), 8.25 (s, 0.5H), 8.19 (s, 0.5H), 8.17-8.09
(m, 1H), 7.63-7.50 (m, 1H), 7.41- 7.29 (m, 1H), 4.12 (s, 0.5H),
3.97 (dq, J = 14.2, 7.0 Hz, 0.5H), 3.46- 3.26 (m, 1H), 3.26-3.05
(m, 2H), 2.75-2.64 (m, 0.5H), 2.64- 2.49 (m, 3.5H), 1.30-1.11 (m,
6H) .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 174.8, 174.5, 141.5,
138.4, 138.4, 137.5, 137.5, 131.2, 131.0, 128.0, 126.1, 126.1,
124.0, 123.4, 115.0, 114.9, 59.4, 57.3, 43.7, 43.4, 39.4, 39.2,
32.0, 31.7, 18.4, 18.1, 12.9, 12.7 IR (thin film) 3413, 3084, 1657,
1499, 1434 cm.sup.-1 F7 ##STR00090## White Solid 425 ([M +
H].sup.+) (400 MHz, CDCl.sub.3) .delta. 8.85 (t, J = 1.8 Hz,
0.55H), 8.81 (t, J = 1.8 Hz, 0.45H), 8.27-8.13 (m, 2H), 7.67-7.58
(m, 0.55H), 7.56-7.47 (m, 0.45H), 7.45-7.32 (m, 1H), 4.19 (br. s,
0.45H), 4.05 (q, J = 6.8 Hz, 0.55H), 4.01-3.69 (m, 2H), 3.69-3.51
(m, 1H), 3.51- 3.34 (m, 0.45H), 3.19 (dq, J = 14.4, 10.1 Hz,
0.55H), 1.53 (d, J = 6.8 Hz, 1.65H), 1.36 (d, J = 7.1 Hz, 1.35H),
1.24-1.13 (m, 3H) IR (thin film) 2967, 2939, 1665, 1500 cm.sup.-1
F8 ##STR00091## White Solid 441 ([M + H].sup.+) (400 MHz,
CDCl.sub.3) .delta. 8.77 (t, J = 1.8 Hz, 1H), 8.22-8.16 (m, 2H),
7.53 (d, J = 8.5 Hz, 1H), 7.39 (dd, J= 8.5, 6.4 Hz, 1H), 4.31-4.16
(m, 1H), 4.16-3.91 (m, 3H), 3.62- 3.43 (m, 1H), 1.66 (d, J = 7.0
Hz, 3H), 1.37-1.10 (m, 3H) IR (thin film) 2922, 2851, 1661, 1499
cm.sup.-1 F9 ##STR00092## Clear Semi- Solid 357 ([M + H].sup.+)
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.83 (t, J = 1.8 Hz, 1H),
8.25- 8.11 (m, 2H), 7.61 (ddd, J = 8.5, 2.1, 0.9 Hz, 1H), 7.39 (dd,
J = 8.5, 6.5 Hz, 1H), 3.87-3.60 (m, 2H), 3.15 (dt, J = 13.1, 7.7
Hz, 1H), 2.88 (dt, J = 12.9, 6.2 Hz, 1H), 2.79-2.62 (m, 2H), 2.60
(s, 3H), 1.16 (t, J = 7.2 Hz, 3H) .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 170.3, 141.6, 138.3, 137.6, 130.8, 127.3,
126.2, 124.1, 115.1, 49.6, 44.1, 39.0, 27.0, 13.0 F10 ##STR00093##
Orange Oil 355 ([M + H].sup.+) (400 MHz, CDCl.sub.3) .delta. 8.72
(t, J = 1.8 Hz, 1H), 8.16 (ddd, J = 6.5, 1.7, 0.9 Hz, 1H), 8.00 (s,
1H), 7.58 (ddd, J = 8.5, 2.1, 0.9 Hz 1H), 7.38 (dd, J = 8.5, 6.5
Hz, 1H), 3.82 (br. s, 1H), 3.60 (br. s, 1H), 2.85 (dd, J = 12.7,
9.1 Hz, 1H), 2.63 (dt, J = 9.0, 6.5 Hz, 1H), 2.47 (dd, J = 12.7,
5.3 Hz, 1H), 2.02 (s, 3H), 1.22-1.09 (m, 6H) .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 175.4, 142.1, 138.3, 137.5, 130.6, 127.3,
126.2, 124.9, 114.8, 43.8, 38.7, 37.3, 18.3, 16.6, 13.1 F11
##STR00094## Off- White Solid mp = 179-180 449 ([M + H].sup.+) (400
MHz, CDCl.sub.3) .delta. 8.74 (t, J = 1.8 Hz, 1H), 8.18 (ddd, J =
6.5, 1.7, 0.9 Hz, 1H), 8.04 (s, 1H), 7.58 (ddd, J = 8.5, 2.0, 0.8
Hz, 1H), 7.39 (dd, J = 8.5, 6.4 Hz, 1H), 3.71 (m, 2H), 3.43 (m 2H),
3.29 (dd, J = 14.7, 6.9 Hz, 1H), 3.16-2.96 (m, 1H), 2.70 (t, J =
6.8 Hz, 2H), 2.12-1.93 (m, 1H), 1.74 (tdd, J = 11.5, 8.3, 5.3 Hz,
1H), 1.44 (dtd, J = 12.2, 7.9, 3.8 Hz, 1H), 1.16 (t, J = 7.2 Hz,
3H) F12 ##STR00095## Clear Oil 388 ([M + H].sup.+) (400 MHz,
CDCl.sub.3) .delta. 8.76 (t, J = 1.6 Hz, 1H), 8.20 (s, 1H), 8.17
(ddd, J = 6.5, 1.6, 0.8 Hz, 1H), 7.55 (dt, J = 8.6, 4.3 Hz, 1H),
7.37 (dd, J = 8.4, 6.5 Hz, 1H), 4.10 (s, 1H), 3.80 (dd, J = 13.4,
11.1 Hz, 1H), 3.40-3.15 (m, 2H), 2.95 (s, 3H), 2.87 (dd, J = 13.5,
2.4 Hz, 1H), 1.20 (d, J = 7.0 Hz, 3H), 1.16 (t, J = 7.2 Hz, 3H) IR
(thin film) 1657 cm.sup.-1 F13 ##STR00096## White Solid mp =
154-157 455 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.79 (t, J = 1.8 Hz, 1H), 8.19 (ddd, J = 6.4, 1.7, 0.9 Hz,
1H), 8.09 (s, 1H), 7.61 (ddd, J = 8.5, 2.1, 0.9 Hz, 1H), 7.40 (dd,
J = 8.5, 6.5 Hz, 1H), 3.72 (q, J = 7.1 Hz, 2H), 3.52-3.36 (m, 2H),
3.36- 3.21 (m, 2H), 2.81-2.59 (m, 4H), 1.17 (t, J = 7.2 Hz, 3H)
.sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -65.9. P1 ##STR00097##
mp 124-125 409 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.69 (s, 1H), 8.17 (d, J = 6.4 Hz, 1H), 7.95 (s, 1H), 7.56
(d, J = 8.4 Hz, 1H), 7.39 (dd, J = 8.4, 6.4 Hz, 1H), 3.24 (s, 3H),
2.85 (t, J = 6.8 Hz, 2H), 2.69-2.65 (m, 2H), 2.45 (t, J = 7 .6 Hz,
2H), 2.40- 2.34 (m, 2H) P2 ##STR00098## mp 146-147 425 ([M +
H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.70 (s, 1H),
8.17 (d, J = 6.0 Hz, 1H), 8.05 (s, 1H), 7.55 (d, J = 8.4 Hz, 1H),
7.38 (dd, J = 8.4, 6.4 Hz, 1H), 3.26 (s, 3H), 3.21-3.14 (m, 1H),
3.00-2.83 (m, 3H), 2.77- 2.64 (m, 2H), 2.62-2.55 (m, 2H) P9
##STR00099## 433 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.69 (s, 1H), 8.18 (d, J = 6.4 Hz, 1H), 8.07 (s, 1H), 7.60
(dd, J = 8.4, 1.6 Hz, 1H), 7.40 (dd, J = 8.4, 6.4 Hz, 1H),
4.46-4.45 (bs, 2H), 2.85 (t, J = 6.8 Hz, 2H), 2.69- 2.65 (m, 2H),
2.46 (t, J = 7.2 Hz, 2H), 2.41-2.34 (m, 2H), 2.28 (t, J = 2.4 Hz,
1H) IR (KBr) 3421, 3292, 3095, 2929, 2376, 2117, 1676, 1612, 1558
cm.sup.-1 P10 ##STR00100## 449 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.72 (s, 1H), 8.18 (d, J = 6.4 Hz, 1H),
8.16 (s, 1H), 7.60 (dd, J = 8.4, 1.2 Hz, 1H), 7.40 (dd, J = 8.4,
6.4 Hz, 1H), 4.46-4.42 (bs, 2H), 3.21-3.14 (m, 1H), 2.99-2.83 (m,
3H), 2.74-2.70 (m, 2H), 2.66- 2.55 (m, 2H), 2.30 (t, J = 2.4 Hz,
1H) IR (KBr) 3392, 3305, 3290, 3253, 2978, 2358, 2117, 1674, 1612
cm.sup.-1 P18 ##STR00101## 403 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.70 (t, J = 1.6 Hz, 1H), 8.13 (dd, J =
6.4, 0.8 Hz, 1H), 7.80 (s, 1H), 7.55 (dd, J = 8.4, 1.6 Hz, 1H),
7.35 (dd, J = 8.4, 6.4 Hz, 1H), 3.68 (q, J = 7.2 Hz, 2H), 2.84 (t,
J = 6.8 Hz, 2H), 2.67-2.63 (m, 2H), 2.39-2.33 (m, 4H), 2.25 (s,
3H), 1.13 (t, J = 7.2 Hz, 3H) IR (KBr) 3446, 3095, 2970, 2926,
2364, 1647, 1610, 1570, 1398 cm.sup.-1 P19 ##STR00102## 419 ([M +
H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.72 (t, J =
1.6 Hz, 1H), 8.13 (dd, J = 6.4, 0.8 Hz, 1H), 7.89 (s, 1H), 7.55
(dd, J = 8.4, 1.2 Hz, 1H), 7.35 (dd, J = 8.4, 6.4 Hz, 1H) ,
3.80-3.60 (bs, 2H), 3.19-3.12 (m, 1H), 2.99-2.81 (m, 3H), 2.67-
2.54 (m, 4H), 2.27 (s, 3H), 1.15 (t, J = 7.2 Hz, 3H) IR (KBr) 3421,
3095, 2978, 2856, 2374, 2310, 1647, 1570, 1506 cm.sup.-1 P36
##STR00103## 441 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.55 (s, 1H), 8.11 (t, J = 2.0 Hz, 1H), 7.91 (s, 1H), 7.46
(ddd, J = 8.0, 3.2, 1.6 Hz, 1H), 3.70 (q, J = 7.2 Hz, 2H), 2.84 (t,
J = 6.8 Hz, 2H), 2.68-2.64 (m, 2H), 2.43- 2.33 (m, 4H), 1.13 (t, J
= 7.2 Hz, 3H) IR (KBr) 3093, 2978, 2935, 2875, 1660, 1651, 1622,
1583, 1497 cm.sup.-1 P37 ##STR00104## 457 ([M + H].sup.+) .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.58 (s, 1H), 8.11 (dd, J = 5.6,
2.0 Hz, 1H), 8.04 (s, 1H), 7.46 (ddd, J = 8.4, 3.6, 2.0 Hz, 1H),
3.76- 3.65 (m, 2H), 3.20-3.13 (m, 1H), 2.99-2.82 (m, 3H), 2.69-2.54
(m, 4H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr) 3078, 2978, 2933, 1616,
1583, 1575, 1435, 1361 cm.sup.-1 P48 ##STR00105## mp 109-111 417
([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.68 (s,
1H), 8.17 (d, J = 6.4 Hz, 1H), 7.90 (s, 1H), 7.56 (dd, J = 8.4, 1.2
Hz, 1H), 7.39 (dd, J = 8.4, 6.4 Hz, 1H), 3.71 (q, J = 7.2 Hz, 2H),
2.86 (t, J = 7.2 Hz, 2H), 2.60 (d, J = 7.2 Hz, 2H), 2.42 (t, J =
7.6 Hz, 2H), 1.79-1.71 (m, 1H), 1.53-1.44 (m, 1H), 1.15 (t, J = 7.2
Hz, 3H), 1.08-1.02 (m, 1H) P49 ##STR00106## 433 ([M + H].sup.+)
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.77 (s, 1H), 8.17 (d, J
= 6.4 Hz, 1H), 8.11 (s, 1H), 7.60 (dd, J = 8.4, 1.2 Hz, 1H), 7.38
(dd, J = 8.4, 6.4 Hz, 1H), 3.76-3.67 (m, 2H), 3.17-3.15 (m, 1H),
2.94-2.81 (m, 3H), 2.69-2.62 (m, 2H), 2.10- 1.91 (m, 1H), 1.71-1.65
(m, 1H), 1.34-1.27 (m, 1H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr) 3088,
2978, 2933, 2910, 2875, 2378, 1716, 1695, 1668, 1653, 1633, 1614
cm.sup.-1 P50 ##STR00107## mp 144-148 409 ([M + H].sup.+) .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.84 (t, J = 1.8 Hz, 1H), 8.18
(ddd, J = 6.4, 1.7, 0.9 Hz, 1H), 8.05 (s, 1H), 7.63 (ddd, J = 8.5,
2.1, 0.9 Hz, 1H), 7.41 (dd, J = 8.5, 6.4 Hz, 1H), 3.71 (q, J = 7.2
Hz, 2H), 3.11 (q, J = 9.9 Hz, 2H), 2.96 (t, J = 7.0 Hz, 2H), 2.45
(t, J = 7.0 Hz, 2H), 1.16 (t, J = 7.2 Hz, 3H) .sup.19F NMR (376
MHz, CDCl.sub.3) .delta. -66.6 P53 ##STR00108## mp 89-91 437 ([M +
H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.69 (s, 1H),
8.17 (d, J = 6.4 Hz, 1H), 7.91 (s, 1H), 7.56 (dd, J = 8.4, 1.2 Hz,
1H), 7.39 (dd, J = 8.4, 6.4 Hz, 1H), 3.69 (q, J = 7.2 Hz, 2H), 2.80
(d, J = 7.2 Hz, 2H), 2.56 (d, J = 6.8 Hz, 2H), 2.40 (d, J = 7.2 Hz,
2H), 2.23-2.12 (m, 2H), 1.86-1.80 (m, 2H), 1.17 (t, J = 7.2 Hz, 3H)
P54 ##STR00109## 453 ([M + H].sup.+) .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.73 (s, 1H), 8.17 (d, J = 6.4 Hz, 1H), 8.03
(s, 1H), 7.56 (dd, J = 8.4, 1.6 Hz, 1H), 7.38 (dd, J = 8.4, 6.4 Hz,
1H), 3.76-3.66 (m, 2H), 3.15-3.10 (m, 1H), 2.89-2.86 (m, 1H),
2.78-2.74 (m, 2H), 2.68- 2.62 (m, 2H), 2.33-2.26 (m, 2H), 2.13-2.04
(m, 2H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr) 3990, 3444, 3417, 3086,
2998, 2937, 2871, 1660, 1651, 1614, 1568 cm-1 P56 ##STR00110## 403
([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.69 (s,
1H), 8.17 (d, J = 6.4 Hz, 1H), 7.95 (s, 1H), 7.57 (dd, J = 8.4, 1.2
Hz, 1H), 7.39 (dd, J = 8.4, 6.8 Hz, 1H), 3.24 (s, 3H), 2.87 (t, J =
7.2 Hz, 2H), 2.61 (d, J = 7.6 Hz, 2H), 2.47 (t, J = 7.2 Hz, 2H),
1.81-1.70 (m, 1H), 1.53-1.44 (m, 1H), 1.09-1.01 (m, 1H) IR (KBr)
3089, 3032 , 2918, 2850 1676, 1570, 1560, 1471, 1456 cm.sup.-1 P57
##STR00111## 419 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.72 (s, 1H), 8.17 (d, J = 6.4 Hz, 1H), 8.08 (d, J = 2.4
Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.38 (dd, J = 8.4, 6.4 Hz, 1H),
3.26 (s, 3H), 3.23-3.11 (m, 1H), 2.96-2.77 (m, 3H), 2.75-2.63 (m,
2H), 2.05- 1.93 (m, 1H), 1.73-1.66 (m, 1H), 1.37-1.28 (m, 1H) IR
(KBr) 3446, 3095, 2924, 1670, 1653, 1647, 1610, 1570 cm.sup.-1 P62
##STR00112## mp 102-104 423 ([M + H].sup.+) .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.68 (s, 1H), 8.17 (d, J = 6.4 Hz 1H), 7.93 (s,
1H), 7.54 (dd, J = 8.4, 1.2 Hz, 1H), 7.40 (dd, J = 8.4, 6.4 Hz,
1H), 3.24 (s, 3H), 2.81 (d, J = 7.2 Hz, 2H), 2.56 (d, J = 6.8 Hz,
2H), 2.43 (d, J = 7.2 Hz, 2H), 2.23-2.13 (m, 2H), 1.87-1.79 (m, 2H)
P63 ##STR00113## 439 ([M + H].sup.+) .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.71 (s, 1H), 8.17 (d, J = 6.4 Hz, 1H), 8.06
(s, 1H), 7.54 (d, J = 8.4 Hz, 1H), 7.38 (dd, J = 8.4, 6.4 Hz, 1H),
3.26 (s, 3H), 3.18-3.08 (m, 1H), 2.92-2.86 (m, 1H), 2.79- 2.62 (m,
4H), 2.36-2.24 (m, 2H), 2.14-2.06 (m, 2H) IR (KBr) 3093, 2920,
2850, 2376, 2310, 1663, 1616, 1498, 1356 cm.sup.-1 P65 ##STR00114##
427 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.71
(s, 1H), 8.19 (d, J = 6.4 Hz, 1H), 8.07 (s, 1H), 7.61 (dd, J = 6.4,
1.2 Hz, 1H), 7.40 (dd, J = 8.4, 6.4 Hz, 1H), 4.46 (bs, 2H), 2.88
(t, J = 7.2 Hz, 2H), 2.61 (d, J = 7.6 Hz, 2H), 2.48 (t, J = 7.2 Hz,
2H), 2.27 (t, J = 2.4 Hz, 1H), 1.80- 1.70 (m, 1H), 1.54-1.43 (m,
1H), 1.09-1.01 (m, 1H) IR (KBr) 3253, 3095, 2924, 2852, 2376, 2320,
1676, 1612, 1570 cm.sup.-1 P66 ##STR00115## 443 ([M + H].sup.+)
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.72 (s, 1H), 8.18 (d, J
= 6.4 Hz, 1H), 8.17 (s, 1H), 7.60 (dd, J = 8.4, 1.6 Hz, 1H), 7.39
(dd, J = 8.4, 6.4 Hz, 1H), 3.23-3.11 (m, 1H), 2.96-2.79 (m, 3H),
2.76-2.67 (m, 2H), 2.29 (s, 3H), 2.08-1.89 (m, 1H), 1.73-1.67 (m,
1H), 1.37- 1.28 (m, 1H) IR (KBr) 3460, 3427, 3244, 3089, 3012,
2968, 2924, 2117, 1672, 1612, 1568 cm.sup.-1 P71 ##STR00116## 447
([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.69 (s,
1H), 8.18 (d, J = 6.4 Hz, 1H), 8.07 (s, 1H), 7.59 (dd, J = 8.4, 1.2
Hz, 1H), 7.39 (dd, J = 8.4, 6.4 Hz, 1H), 4.45 (d, J = 2.4 Hz, 2H),
2.81 (d, J = 7.2 Hz, 2H), 2.56 (d, J = 6.8 Hz, 2H), 2.45 (d, J =
7.2 Hz, 2H), 2.27 (t, J = 2.4 Hz, 1H), 2.21-2.15 (m, 2H), 1.86-
1.80 (m, 2H) IR (KBr) 3431, 3385, 3307, 2933, 2873, 2263, 1674,
1612, 1568, 1386, 1356 cm.sup.-1 P72 ##STR00117## 463 ([M +
H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.71 (s, 1H),
8.18 (d, J = 6.4 Hz, 1H), 8.16 (s, 1H), 7.59 (dd, J = 8.4, 0.8 Hz,
1H), 7.39 (dd, J = 8.4, 6.4 Hz, 1H), 4.48-4.44 (bs, 2H),
3.18-3.11 (m, 1H), 2.94-2.87 (m, 1H), 2.77 (t, J = 7.6 Hz, 2H),
2.72-2.66 (m, 2H), 2.35-2.24 (m, 3H), 2.13-2.06 (m, 2H) IR (KBr)
3415, 3240, 3084, 2931, 2345, 2117, 1678, 1612, 1566 cm.sup.-1 P74
##STR00118## 397 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.71 (s, 1H), 8.13 (d, J = 6.4 Hz, 1H), 7.80 (s, 1H), 7.56
(dd, J = 8.4, 1.6 Hz, 1H), 7.35 (dd, J = 8.4, 6.4 Hz, 1H), 3.68
(bs, 2H), 2.86 (t, J = 7.2 Hz, 2H), 2.59 (d, J = 7.6 Hz, 2H), 2.37
(t, J = 7.2 Hz, 2H), 2.25 (s, 3H), 1.79-1.69 (m, 1H), 1.40-1.56 (m,
1H), 1.13 (t, J = 7.2 Hz, 3H), 1.08-1.00 (m, 1H) IR (KBr) 3392,
3103, 2933, 2368, 2322, 1662, 1614, 1571, 1504 cm.sup.-1 P75
##STR00119## 413 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.72 (s, 1H), 8.13 (d, J = 6.4 Hz, 1H), 7.89 (d, J = 1.6
Hz, 1H), 7.56 (dd, J = 8.4, 1.6 Hz, 1H), 7.35 (dd, J = 8.4, 6.4 Hz,
1H), 3.69-3.67 (bs, 2H), 3.19-3.09 (m, 1H), 2.92-2.80 (m, 3H),
2.67- 2.54 (m, 2H), 2.28 (s, 3H), 2.08- 1.93 (m, 1H), 1.71-1.64 (m,
1H), 1.37-1.29 (m, 1H), 1.15 (t, J = 7.2 Hz, 3H) IR (KBr) 3421,
3095, 2974, 2926, 2773, 2308, 1647, 1612, 1570, 1506 cm.sup.-1 P80
##STR00120## 417 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.70 (s, 1H), 8.13 (d, J = 6.4 Hz, 1H), 7.80 (s, 1H), 7.54
(dd, J = 8.4, 1.2 Hz, 1H), 7.35 (dd, J = 8.4, 6.4 Hz, 1H), 3.68 (q,
J = 7.2 Hz, 2H), 2.79 (d, J = 7.2 Hz, 2H), 2.55 (d, J = 6.8 Hz,
2H), 2.35 (d, J = 7.2 Hz, 2H), 2.25 (s, 3H), 2.21- 2.15 (m, 2H),
1.86-1.80 (m, 2H), 1.15 (t, J = 7.2 Hz, 3H) IR (KBr) 3084, 2937,
1664, 1568, 1500, 1440, 1417, 1386, 1356 cm.sup.-1 P81 ##STR00121##
433 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.72
(t, J = 2.0 Hz, 1H), 8.13 (d, J = 6.4 Hz, 1H), 7.89 (s, 1H), 7.56
(dd, J = 8.4, 1.2 Hz, 1H), 7.35 (dd, J = 8.4, 6.4 Hz, 1H), 3.80-
3.60 (bs, 2H), 3.16-3.09 (m, 1H), 2.89-2.82 (m, 1H), 2.80- 2.74 (m,
2H), 2.70-2.52 (m, 2H), 2.33-2.28 (m, 2H), 2.26 (s, 3H), 2.13-2.06
(m, 2H), 1.14 (t, J = IR (KBr) 3444, 3417, 3093, 2978, 2679, 2353,
2320, 1660, 1651, 1573 cm.sup.-1 7.2 Hz, 3H) P92 ##STR00122## 435
([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.57 (s,
1H), 8.10 (t, J = 2.0 Hz, 1H), 7.94 (s, 1H), 7.46 (dd, J = 8.0, 2.0
Hz, 1H), 3.70 (q, J = 7.2 Hz, 2H), 2.86 (t, J = 7.2 Hz, 2H), 2.60
(d, J = 7.2 Hz, 2H), 2.48 (t, J = 7.6 Hz, 2H), 1.79-1.71 (m, 1H),
1.53-1.44 (m, 1H), 1.15 (t, J = 7.2 Hz, 3H), 1.09-1.01 (m, 1H) IR
(KBr) 3093, 2978, 2933, 1668, 1645, 1622, 1583, 1575 cm.sup.-1 P93
##STR00123## 451 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.60 (s, 1H), 8.10 (t, J = 2.0 Hz, 1H), 8.04 (s, 1H), 7.45
(dd, J = 7.6, 2.0 Hz, 1H), 3.76-3.66 (m, 2H), 3.17-3.15 (m, 1H),
2.94- 2.81 (m, 3H), 2.69-2.62 (m, 2H), 2.10-1.91 (m, 1H), 1.71-1.65
(m, 1H) , 1.34-1.27 (m, 1H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr)
3429, 3093, 3078, 2978, 2926, 2355, 2328, 1668, 1622, 1585
cm.sup.-1 P98 ##STR00124## 455 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.57 (s, 1H), 8.11 (dd, J = 3.6, 1.6 Hz,
1H), 7.92 (s, 1H), 7.46 (ddd, J = 8.0, 3.6, 1.6 Hz, 1H), 3.69 (q, J
= 7.2 Hz, 2H), 2.80 (d, J = 7.2 Hz, 2H), 2.56 (d, J = 6.8 Hz, 2H),
2.39 (d, J = 7.2 Hz, 2H), 2.26- 2.12 (m, 2H), 1.88-1.79 (m, 2H),
1.17 (t, J = 7.2 Hz, 3H) IR (KBr) 3462, 3446, 3427, 3093, 2976,
2935, 2875, 1670, 1622, 1583 cm.sup.-1 P99 ##STR00125## 471 ([M +
H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.57 (s, 1H),
8.11 (dd, J = 3.6, 1.6 Hz, 1H), 7.92 (s, 1H), 7.46 (ddd, J = 8.0,
3.6, 1.6 Hz, 1H), 3.76- 3.66 (m, 2H), 3.15-3.10 (m, 1H), 2.89-2.86
(m, 1H), 2.78-2.74 (m, 2H), 2.68-2.62 (m, 2H), 2.33- 2.26 (m, 2H),
2.13-2.04 (m, 2H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr) 3446, 3419,
3209, 3060, 2978, 2877, 1670, 1624, 1585, 1356 cm.sup.-1 FA1
##STR00126## 417 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.75 (s, 1H), 8.14 (d, J = 6.4 Hz, 1H), 7.85 (s, 1H), 7.59
(dd, J = 8.4, 1.2 Hz, 1H), 7.37 (dd, J = 8.4, 6.4 Hz, 1H),
3.82-3.50 (bs, 2H), 2.89 (t, J = 6.4 Hz, 1H), 2.68- 2.64 (m, 3H),
2.63-2.60 (m, 1H), 2.56-2.32 (m, 2H), 2.28 (s, 3H), 1.14 (t, J =
7.2 Hz, 6H) IR (KBr) 3091, 2974, 2931, 2875, 2866, 1645, 1614,
1573, 1558, 1504, 1398 cm.sup.-1 FA2 ##STR00127## 455 ([M +
H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.48 (s, 1H),
8.07 (dd, J = 3.6, 1.6 Hz, 1H), 7.87 (s, 1H), 7.39 (ddd, J = 8.0,
3.6, 1.6 Hz, 1H), 3.82- 3.80 (bs, 1H), 3.78-3.76 (bs, 1H), 2.89 (t,
J = 6.4 Hz, 1H), 2.73- 2.51 (m, 4H), 2.41-2.30 (m, 2H), 1.16 (t, J
= 7.2 Hz, 6H) IR (KBr) 3091, 2976, 2935, 2875, 1649, 1622, 1585,
1494, 1460, 1431 cm.sup.-1 FA3 ##STR00128## 437 ([M + H].sup.+)
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.70 (s, 1H), 8.17 (d, J
= 6.4 Hz, 1H), 7.95 (s, 1H), 7.56 (dd, J = 8.4, 1.2 Hz, 1H), 7.38
(dd, J = 8.4, 6.4 Hz, 1H), 3.82-3.64 (bs, 1H), 3.58-3.49 (bs, 1H),
2.88 (t, J = 6.8 Hz, 1H), 2.68-2.51 (m, 4H), 2.41-2.32 (m, 2H),
1.16 (t, J = 7.2 Hz, 6H) IR (KBr) 3088, 2976, 2933, 2875, 2854,
1660, 1653, 1612, 1566, 1498 cm.sup.-1 FA4 ##STR00129## mp 132-136
447 ([M + H].sup.+) .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta.
9.05 (s, 1H), 8.84 (s, 1H), 8.22 (dd, J = 6.4, 0.8 Hz, 1H), 7.82
(dd, J = 8.8, 2.0 Hz, 1H), 7.57 (dd, J = 8.4, 6.4 Hz, 1H), 4.49-
4.41 (bs, 1H), 4.39-4.30 (bs, 1H), 3.24 (t, J = 2.0 Hz, 1H), 2.78-
2.72 (m, 1H), 2.65-2.60 (m, 1H), 2.54-2.40 (m, 5H), 1.06 (t, J =
6.8 Hz, 3H) FA5 ##STR00130## 423 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.70 (s, 1H), 8.17 (d, J = 6.4 Hz, 1H),
7.97 (s, 1H), 7.56 (dd, J = 8.4, 1.2 Hz, 1H), 7.39 (dd, J = 8.4,
6.4 Hz, 1H), 3.25 (s, 3H), 2.88 (t, J = 6.8, 1H), 2.72-2.52 (m,
4H), 2.39-2.32 (m, 2H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr) 3089,
2974, 2933, 2975, 2854, 1714, 1666, 1660, 1651, 1643, 1614
cm.sup.-1 FA6 ##STR00131## 471 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.56 (d, J = 1.2 Hz, 1H), 8.16 (dd, J =
3.6, 1.2 Hz, 1H), 8.08 (dd, J = 6.0, 2.0 Hz, 1H), 7.39 (dd, J =
6.0, 2.0 Hz, 1H), 4.15- 3.95 (bs, 1H), 3.23-3.14 (m, 1H), 3.13-3.11
(m, 2H), 2.96-2.56 (m, 5H), 1.23 (t, J = 7.2 Hz, 3H), 1.15 (m, 3H)
IR (KBr) 3446, 3080, 2978, 2937, 2358, 1662, 1622, 1585, 1496
cm.sup.-1 FA7 ##STR00132## 463 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.72 (d, J = 1.2 Hz, 1H), 8.26 (d, J = 4.8
Hz, 1H), 8.15 (d, J = 5.2 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 7.36
(dd, J = 6.0, 2.0 Hz, 1H), 5.00-4.72 (bs, 1H), 4.20-3.90 (bs, 1H),
3.30-3.10 (m, 2H), 2.95-2.68 (m, 2H), 2.65-2.45 (m, 3H), 2.26 (t, J
= 2.4 Hz, 1H), 1.25 (t, J = 7.2 Hz, 3H) IR (KBr) 3441, 3419, 3084,
2976, 2924, 2852, 2351, 2119, 1714, 1668, 1651, 1614 cm.sup.-1 FA8
##STR00133## 439 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.72 (d, J = 1.2 Hz, 1H), 8.26 (d, J = 4.8 Hz, 1H), 8.16
(d, J = 5.2 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 7.36 (dd, J = 6.0,
2.0 Hz, 1H), 3.28 (s, 3H), 3.30-3.10 (m, 2H), 2.95-2.80 (m, 2H),
2.70-2.45 (m, 3H), 1.25 (t, J = 7.2 Hz, 3H) IR (KBr) 3444, 3080,
2924, 2357, 2332, 1662, 1653, 1614, 1568 cm.sup.-1 FA9 ##STR00134##
453 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.75
(d, J = 1.2 Hz, 1H), 8.20 (d, J = 4.8 Hz, 1H), 8.16 (d, J = 5.2 Hz,
1H), 7.58 (d, J = 8.4 Hz, 1H), 7.36 (dd, J = 6.0, 2.0 Hz, 1H),
4.15-3.95 (bs, 1H), 3.23-3.14 (m, 1H), 3.13-3.11 (m, 2H), 2.96-
2.56 (m, 5H), 1.23 (t, J = 7.2 Hz, 3H), 1.15 (m, 3H) IR (KBr) 3084,
2978, 2935, 2877, 2310, 1645, 1614, 1558, 1539, 1489 cm.sup.-1 FA10
##STR00135## 433 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.73 (d, J = 1.2 Hz, 1H), 8.11 (d, J = 4.8 Hz, 1H), 7.59
(d, J = 5.2 Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.33 (dd, J = 6.0,
2.0 Hz, 1H), 3.90 (bs, 1H), 3.40-3.30 (m, 1H), 3.25-3.05 (m, 2H),
2.96- 2.56 (m, 5H), 2.30 (s, 3H), 1.33- 1.10 (m, 6H) IR (KBr) 3088,
2972, 2927, 2378, 2347, 1645, 1612, 1570, 1558, 1543, 1506
cm.sup.-1 FA11 ##STR00136## 359 ([M + H].sup.+) .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.73 (t, J = 1.8 Hz, 1H), 8.23- 8.12 (m,
2H), 7.53 (ddd, J = 8.5, 2.0, 0.9 Hz, 1H), 7.38 (dd, J = 8.5, 6.5
Hz, 1H), 4.04-3.61 (m, 4H), 3.18 (d, J = 0.9 Hz, 3H), 1.20 (t, J =
7.2 Hz, 3H) IR (KBr) 3097, 1660 cm.sup.-1 FA12 ##STR00137## 359 ([M
+ H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.73 (t, J =
1.8 Hz, 1H), 8.23 (s, 1H), 8.18 (ddd, J = 6.4, 1.6, 0.9 Hz, 1H),
7.52 (ddd, J = 8.5, 2.0, 0.9 Hz, 1H), 7.38 (dd, J = 8.5, 6.4 Hz,
1H), 3.99 (qd, J = 7.0, 0.9 Hz, 1H), 3.31 (s, 3H), 3.01 (d, J = 0.8
Hz, 3H), 1.64 (d, J = 7.0 Hz, 3H) IR (KBr) 3097, 1662 cm.sup.-1
FA13 ##STR00138## 373 ([M + H].sup.+) .sup.1H NMR (500 MHz,
CDCl.sub.3) .delta. 8.73 (d, J = 1.9 Hz, 1H), 8.23- 8.09 (m, 2H),
7.56-7.47 (m, 1H), 7.38 (dd, J = 8.5, 6.4 Hz, 1H), 4.00 (dd, J =
13.5, 7.0 Hz, 1H), 3.91 (q, J = 7.0 Hz, 1H), 3.50 (dd, J = 13.8,
7.4 Hz, 1H), 3.00 (s, 3H), 1.64 (d, J = 7.0 Hz, 3H), 1.20 (t, J =
7.2 Hz, 3H) IR (KBr) 3397, 1663 cm.sup.-1 FA14 ##STR00139## 399 ([M
+ H].sup.+) .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 8.72 (t, J =
1.8 Hz, 1H), 8.26- 8.09 (m, 2H), 7.59-7.47 (m, 1H), 7.38 (dd, J =
8.5, 6.5 Hz, 1H), 3.94 (q, J = 7.0 Hz, 1H), 3.83 (dd, J = 13.9, 7.1
Hz, 1H), 3.36 (dd, J = 13.9, 7.4 Hz, 1H), 2.99 (s, 3H), 1.65 (d, J
= 7.0 Hz, 3H), 0.98 (tt, J = 7.6, 4.7 Hz, 1H), 0.60-0.49 (m, 2H),
0.27-0.15 (m, 2H) IR (KBr) 3083, 1664 cm.sup.-1
TABLE-US-00004 TABLE 4 Prepared according to No. Structure
Appearance Example: C1 ##STR00140## Tan Solid 1 C3 ##STR00141##
Brown, Highly Viscous Oil 3 C4 ##STR00142## Yellow Oil 4 C6
##STR00143## White Solid 7 C7 ##STR00144## Color-less Gum 8 C8
##STR00145## Clear, Color-less Oil 10 C9 ##STR00146## Pale Yellow
Solid 13 CA1 ##STR00147## 1 CA2 ##STR00148## Light brown solid 1
CA3 ##STR00149## 1 CA4 ##STR00150## Off-white solid 1 CA5
##STR00151## 17 CA6 ##STR00152## Off-white solid 17 CA7
##STR00153## 17 CA8 ##STR00154## Off-white solid 17 CA9
##STR00155## Colorless liquid 18 CA10 ##STR00156## Colorless liquid
18 CA11 ##STR00157## Liquid 19 CA12 ##STR00158## Liquid 19
TABLE-US-00005 TABLE 5 May be Prepared according to No. Structure
Example: P1 ##STR00159## 11 P2 ##STR00160## 12 P3 ##STR00161## 9 P4
##STR00162## 11 P5 ##STR00163## 12 P6 ##STR00164## 9 P7
##STR00165## 11 P8 ##STR00166## 12 P9 ##STR00167## 11 P10
##STR00168## 12 P11 ##STR00169## 9 P12 ##STR00170## 11 P13
##STR00171## 12 P14 ##STR00172## 9 P15 ##STR00173## 11 P16
##STR00174## 12 P17 ##STR00175## 9 P18 ##STR00176## 11 P19
##STR00177## 12 P20 ##STR00178## 9 P21 ##STR00179## 11 P22
##STR00180## 12 P23 ##STR00181## 9 P24 ##STR00182## 11 P25
##STR00183## 12 P26 ##STR00184## 9 P27 ##STR00185## 15 P28
##STR00186## 12 P29 ##STR00187## 9 P30 ##STR00188## 15 P31
##STR00189## 12 P32 ##STR00190## 11 P33 ##STR00191## 15 P34
##STR00192## 12 P35 ##STR00193## 9 P36 ##STR00194## 11 P37
##STR00195## 12 P38 ##STR00196## 9 P39 ##STR00197## 11 P40
##STR00198## 12 P41 ##STR00199## 9 P42 ##STR00200## 11 P43
##STR00201## 12 P44 ##STR00202## 9 P45 ##STR00203## 11 P46
##STR00204## 12 P47 ##STR00205## 9 P48 ##STR00206## 11 P49
##STR00207## 12 P50 ##STR00208## 11 P51 ##STR00209## 12 P52
##STR00210## 9 P53 ##STR00211## 11 P54 ##STR00212## 12 P55
##STR00213## 9 P56 ##STR00214## 11 P57 ##STR00215## 12 P58
##STR00216## 9 P59 ##STR00217## 11 P60 ##STR00218## 12 P61
##STR00219## 9 P62 ##STR00220## 11 P63 ##STR00221## 12 P64
##STR00222## 9 P65 ##STR00223## 11 P66 ##STR00224## 12 P67
##STR00225## 9 P68 ##STR00226## 11 P69 ##STR00227## 12 P70
##STR00228## 9 P71 ##STR00229## 11 P72 ##STR00230## 12 P73
##STR00231## 9 P74 ##STR00232## 11 P75 ##STR00233## 12 P76
##STR00234## 9 P77 ##STR00235## 11 P78 ##STR00236## 12 P79
##STR00237## 9 P80 ##STR00238## 11 P81 ##STR00239## 12 P82
##STR00240## 9 P83 ##STR00241## 15 P84 ##STR00242## 12 P85
##STR00243## 9 P86 ##STR00244## 15 P87 ##STR00245## 12 P88
##STR00246## 9 P89 ##STR00247## 15 P90 ##STR00248## 12 P91
##STR00249## 9 P92 ##STR00250## 11 P93 ##STR00251## 12 P94
##STR00252## 9 P95 ##STR00253## 11 P96 ##STR00254## 12 P97
##STR00255## 9 P98 ##STR00256## 11 P99 ##STR00257## 12 P100
##STR00258## 9 P101 ##STR00259## 11 P102 ##STR00260## 12 P103
##STR00261## 9 P104 ##STR00262## 11 P105 ##STR00263## 12 P106
##STR00264## 9 P107 ##STR00265## 11 P108 ##STR00266## 12 P109
##STR00267## 9
While this invention has been described in certain embodiments, the
present invention can be further modified within the spirit and
scope of this disclosure. This application is therefore intended to
cover any variations, uses, or adaptations of the invention using
its general principles. Further, this application is intended to
cover such departures from the present disclosure as come within
known or customary practice in the art to which this invention
pertains and which fall within the limits of the appended
claims.
* * * * *